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Chloride content of dissolver solution from Rocky Flats scrub alloy ninth and tenth campaigns following head end treatment

Description: F-Canyon continues to obtain excellent chloride removal from Rocky Flats scrub alloy (RFSA) dissolver solution during head end treatment. One single batch of solution from the ninth RFSA campaign, dissolved in January and February of this year, and two batches from the tenth campaign, dissolved in February, have been successfully processed. Following dissolution in Tank 6.4D, chloride was precipitated with mercurous ion added as the nitrate. The precipitate, Hg{sub 2}Cl{sub 2}, was concurrently removed with the gelatin floc via centrifugation. For each of these three batches processed, a set of duplicate samples was obtained from Tank 11.2 or from Tank 13.3, containing the head end product. The samples were preanalyzed by Laboratories Department for density and acidity to ensure them to be representative of the tank`s contents prior to chloride analysis by the Separations Technology Laboratory. Previous work indicated that in order to protect downstream canyon equipment from chloride attack, the chloride content of RFSA solutions should be less than 100 ppm. All batches from these two RFSA campaigns meet this criterion.
Date: March 8, 1988
Creator: Holcomb, H.P.
Partner: UNT Libraries Government Documents Department

A CAVITY RING-DOWN SPECTROSCOPY MERCURY CONTINUOUS EMISSION MONITOR

Description: SRD tested a number of different length cavities during this past quarter. Continuous transmission was observed with cavity lengths from 65 to 12 cm. The 65 cm cavity was replaced with a 39 cm cavity for work performed during this quarter. Flue gas components were tested for background absorptions and any interference with the determination of accurate mercury concentrations. Sulfur dioxide was found to absorb fairly strongly in the region of the mercury transition, but the Cavity Ring-Down (CRD) instrument was still able to detect mercury at subparts-per-billion by volume (ppb) levels. Additional flue gases tested included H{sub 2}O, CO, CO{sub 2}, NO, NO{sub 2}. None of these flue gas constituents showed any observable absorption in the ultraviolet region near the atomic mercury transition. Work was also initiated in speciation studies. In particular mercury chloride (HgCl{sub 2}) was tested. A mercury signal was detected from a gas stream containing HgCl{sub 2}. SRD was not able to determine definitively if there exists a spectral shift great enough to separate HgCl{sub 2} from elemental mercury in these initial tests.
Date: December 31, 2002
Creator: Carter, Christopher C.
Partner: UNT Libraries Government Documents Department

Chloride content of dissolver solution from Rocky Flats alloy thirteenth campaign following head end treatment

Description: F-Canyon continues to obtain good chloride removal from Rocky Flats Alloy solution during head end treatment. One single batch of solution from the thirteenth alloy campaign, dissolved earlier this month, has been successfully processed. This was the first campaign to combine Rocky Flats Scrub Alloy (RFSA) with Rocky Flats Anode Heel Alloy (RFAHA) in the same dissolution solution (TA-2-1183). Following dissolution in Tank 6.4D, chloride was precipitated with mercurous ion added as the nitrate. The precipitate, Hg{sub 2}Cl{sub 2}, was concurrently removed with the gelatin floc via centrifugation. For this batch, a set of duplicate samples was initially obtained from Tank 11.2. However, due to repeated acid and density measurements by Laboratories, the volume of sample remaining was insufficient to permit chloride analysis. Samples of the same solution, now transferred to Tank 13.3, were analyzed. During the transfer, a 2% dilution occurred, but this error is not significant due to the larger error in the chloride analysis. For the single batch of RFSA-RFAHA material processed from the thirteenth campaign, the head end product contained 52 ppm ({micro}g/mL) chloride, a DF of 22. Relative standard deviation of the measurement was {+-}6 ppm (n = 4) for a precision of {+-}12%.
Date: September 20, 1988
Creator: Holcomb, H. P.
Partner: UNT Libraries Government Documents Department

Chloride content of Rocky Flats scrub alloy eleventh campaign solution following head end treatment

Description: A single batch of dissolver solution from the eleventh Rocky Flats Scrub Alloy (RFSA) campaign has been analyzed for chloride content following head end treatment to reduce its concentration. Scrub alloy buttons were dissolved in Tank 6.4D during May. In subsequent head end processing, chloride was precipitated with mercurous ion added as the nitrate. The precipitate, Hg{sub 2}Cl{sub 2}, was concurrently removed with the gelatin floc via centrifugation. Duplicate samples from Tank 11.2, containing the head end product, produced excellent agreement between their density measurements, acid analyses, and gross alpha activities, indicating them to be truly representative of the tank`s contents. Duplicate aliquots from each of these solutions were analyzed using the turbidimetric chloride method developed in the Separations Technology Laboratory. These resulted in an average chloride value of 41 ppm ({micro}g/mL) chloride for the head end product. Relative standard deviation of the measurement was {+-}4 ppm (n = 4), a precision of {+-}10%. Such a variance is normal at this low chloride level. Since initial chloride values prior to head end averaged 1455 ppm (0.041M), as analyzed by Laboratories Department, a chloride DF of approximately 35 was obtained. Such a reduced chloride level (to less than 100 ppm) in the treated solution will permit further canyon processing with minimal corrosion.
Date: June 30, 1988
Creator: Holcomb, H. P.
Partner: UNT Libraries Government Documents Department

Chloride content of Rocky Flats scrub alloy twelfth campaign solution following head end treatment

Description: A single batch of dissolver solution from the twelfth Rocky Flats Scrub Alloy (RFSA) campaign has been analyzed for chloride content following head end treatment to reduce its concentration. Scrub alloy buttons were dissolved in Tank 6.4D during July. In subsequent head end processing, chloride was precipitated with mercurous ion added as the nitrate. The precipitate, Hg{sub 2}Cl{sub 2}, was co-removed with the gelatin floc via centrifugation. Duplicate samples from Tank 11.2, containing the head end product, produced excellent agreement between their density measurements and acid analyses, indicating them to be truly representative of the tank`s contents. Duplicate aliquots from each of these solutions were analyzed using the turbidimetric chloride method developed in the Separations Technology Laboratory. These resulted in an average chloride value of 53 ppm ({micro}g/mL) chloride for the head end product. Relative standard deviation of the measurement was {+-}6 ppm (n = 4), a precision of {+-}11%. Such a variance is normal at this low chloride level. Since initial chloride values prior to head end averaged 1365 ppm (0.0385M), as analyzed by Laboratories Department, a chloride DF of approximately 26 was obtained. Such a reduced chloride level (to less than 100 ppm) in the treated solution will permit further canyon processing with minimal corrosion.
Date: August 8, 1988
Creator: Holcomb, H. P.
Partner: UNT Libraries Government Documents Department

INVESTIGATION OF THE FATE OF MERCURY IN A COAL COMBUSTION PLUME USING A STATIC PLUME DILUTION CHAMBER

Description: The overall goal of the project was to further develop and then verify SPDC's ability to determine the physical and chemical transformations of mercury in combustion stack plumes. Specific objectives of the project were to perform controlled tests at the pilot scale using dynamic spiking of known mercury compounds (i.e., Hg{sup 0} and HgCl{sub 2}) to prove the ability of the SPDC to determine the following: whether mercury condenses onto particulate matter in a cooling plume; whether there is reduction of Hg{sup 2+} to Hg{sup 0} occurring in hygroscopic aerosols; whether condensed Hg{sup 2+} on particles is photochemically reduced to Hg{sup 0}; and whether or not the Solid Ontario Hydro mercury speciation method (SOH) provides the same results as the Ontario Hydro (OH) mercury speciation method.
Date: November 1, 2001
Creator: Laudal, Dennis L.
Partner: UNT Libraries Government Documents Department

Matrix Isolation Studies of High-Temperature Species Group II Chlorides

Description: A matrix isolation technique for the investigation of infrared absorption spectra of molecules of hightemperature species trapped in a pseudo- gas phase'' is described. The spectra of the dichlorides of zinc, cadmium, and mercury in argon, krypton, and xenon matrices are reported. Presence in the gas phase of dimers of zinc chloride and mercuric chloride is noted. An absorption band, previously reported as due to the degenerate bending motion of zinc chloride, is attributed to zinc dimer. (auth)
Date: September 13, 1962
Creator: McNamee, R. W., Jr.
Partner: UNT Libraries Government Documents Department

Mercury Calibration System

Description: U.S. Environmental Protection Agency (EPA) Performance Specification 12 in the Clean Air Mercury Rule (CAMR) states that a mercury CEM must be calibrated with National Institute for Standards and Technology (NIST)-traceable standards. In early 2009, a NIST traceable standard for elemental mercury CEM calibration still does not exist. Despite the vacature of CAMR by a Federal appeals court in early 2008, a NIST traceable standard is still needed for whatever regulation is implemented in the future. Thermo Fisher is a major vendor providing complete integrated mercury continuous emissions monitoring (CEM) systems to the industry. WRI is participating with EPA, EPRI, NIST, and Thermo Fisher towards the development of the criteria that will be used in the traceability protocols to be issued by EPA. An initial draft of an elemental mercury calibration traceability protocol was distributed for comment to the participating research groups and vendors on a limited basis in early May 2007. In August 2007, EPA issued an interim traceability protocol for elemental mercury calibrators. Various working drafts of the new interim traceability protocols were distributed in late 2008 and early 2009 to participants in the Mercury Standards Working Committee project. The protocols include sections on qualification and certification. The qualification section describes in general terms tests that must be conducted by the calibrator vendors to demonstrate that their calibration equipment meets the minimum requirements to be established by EPA for use in CAMR monitoring. Variables to be examined include linearity, ambient temperature, back pressure, ambient pressure, line voltage, and effects of shipping. None of the procedures were described in detail in the draft interim documents; however they describe what EPA would like to eventually develop. WRI is providing the data and results to EPA for use in developing revised experimental procedures and realistic acceptance criteria based on actual capabilities ...
Date: March 11, 2009
Creator: Schabron, John; Kalberer, Eric; Rovani, Joseph; Sanderson, Mark; Boysen, Ryan & Schuster, William
Partner: UNT Libraries Government Documents Department

Mercury Calibration System

Description: U.S. Environmental Protection Agency (EPA) Performance Specification 12 in the Clean Air Mercury Rule (CAMR) states that a mercury CEM must be calibrated with National Institute for Standards and Technology (NIST)-traceable standards. In early 2009, a NIST traceable standard for elemental mercury CEM calibration still does not exist. Despite the vacature of CAMR by a Federal appeals court in early 2008, a NIST traceable standard is still needed for whatever regulation is implemented in the future. Thermo Fisher is a major vendor providing complete integrated mercury continuous emissions monitoring (CEM) systems to the industry. WRI is participating with EPA, EPRI, NIST, and Thermo Fisher towards the development of the criteria that will be used in the traceability protocols to be issued by EPA. An initial draft of an elemental mercury calibration traceability protocol was distributed for comment to the participating research groups and vendors on a limited basis in early May 2007. In August 2007, EPA issued an interim traceability protocol for elemental mercury calibrators. Various working drafts of the new interim traceability protocols were distributed in late 2008 and early 2009 to participants in the Mercury Standards Working Committee project. The protocols include sections on qualification and certification. The qualification section describes in general terms tests that must be conducted by the calibrator vendors to demonstrate that their calibration equipment meets the minimum requirements to be established by EPA for use in CAMR monitoring. Variables to be examined include linearity, ambient temperature, back pressure, ambient pressure, line voltage, and effects of shipping. None of the procedures were described in detail in the draft interim documents; however they describe what EPA would like to eventually develop. WRI is providing the data and results to EPA for use in developing revised experimental procedures and realistic acceptance criteria based on actual capabilities ...
Date: March 11, 2009
Creator: Schabron, John; Kalberer, Eric; Rovani, Joseph; Sanderson, Mark; Boysen, Ryan & Schuster, William
Partner: UNT Libraries Government Documents Department

Evaluation of preservation methods for selected nutrients in ground water at the Idaho National Engineering Laboratory, Idaho

Description: Water from 28 wells completed in the Snake River Plain aquifer at the Idaho National Engineering Laboratory (INEL) was sampled as part of the US Geological Survey`s quality-assurance program to determine the effect of different preservation methods on nutrient concentrations. Samples were preserved with filtration and with mercuric chloride and chilling, chilling only, or sulfuric acid and chilling. The samples were analyzed for ammonia, nitrite, nitrite plus nitrate, and orthophosphate by the US Geological Survey National Water Quality Laboratory. The study was done in cooperation with the US Department of Energy. The comparison between samples preserved with mercuric chloride and chilling and samples preserved by chilling only showed that all sample pairs were in statistical agreement. Results for ammonia and nitrite plus nitrate samples preserved with sulfuric acid and chilling were within the 95 percent confidence level of the results for the samples preserved by the other two methods and can be considered equivalent to them. Results of this study indicate that discontinuing the use of mercuric chloride as a preservation method for nutrients in water samples will not affect the comparability of data collected at the INEL before and after October 1, 1994.
Date: October 1, 1996
Creator: Bartholomay, R.C. & Williams, L.M.
Partner: UNT Libraries Government Documents Department

A CAVITY RING-DOWN SPECTROSCOPY MERCURY CONTINUOUS EMISSION MONITOR

Description: Accurate reporting of mercury concentration requires a detailed model that includes experimental parameters that vary, such as: pressure, temperature, concentration, absorption cross-section, and isotopic structure etc. During this quarter a theoretical model has been developed to model the 253.7 nm mercury transition. In addition, while testing the interferent species SO{sub 2}, SRD was able to determine the absorption cross-section experimentally and add this to the theoretical model. Assuming that the baseline losses are due to the mirror reflectivity and SO{sub 2}, SRD can now determine the concentrations of both mercury and SO{sub 2} from the data taken. For the CRD instrument to perform as a continuous emission monitor it will be required to monitor mercury concentrations over extended periods of time. The stability of monitoring mercury concentrations over time with the CRD apparatus was tested during the past quarter. During a test which monitored the mercury concentration every 2 seconds it was found that the standard deviation, of a signal from about 1.25 ppb Hg, was only 30 ppt. SRD continued interferent gas testing during this past quarter. This included creating a simulated flue gas composed of the gases tested individually by SRD. The detection limits for mercury, although dependent on the concentration of SO{sub 2} in the simulated gas matrix, remained well below the ppb range. It was determined that for the gases tested the only measurable changes in the baseline level occurred for SO{sub 2} and mercury. Speciation studies continued with mercury chloride (HgCl{sub 2}). This included checking for spectral speciation with both Hg and HgCl{sub 2} present in the CRD cavity. There was no observable spectral shift. Also a pyrolysis oven was incorporated into the gas delivery system both for tests with HgCl{sub 2} as well as atomization of the entire gas stream. The pyrolysis tests conducted ...
Date: April 1, 2003
Creator: Christopher C. Carter, Ph.D.
Partner: UNT Libraries Government Documents Department

REDUCTION OF INHERENT MERCURY EMISSIONS IN PC COMBUSTION

Description: Mercury emission compliance presents one of the major potential challenges raised by the 1990 Clean Air Act Amendments. Simple ways of controlling emissions have not been identified. The variability in the field data suggest that inherent mercury emissions may be reduced if the source of this inherent capture can be identified and controlled. The key mechanisms appear to involve the oxidation of mercury to Hg{sup 2}, generally producing the more reactive HgCl{sub 2}, followed by its capture by certain components of the fly ash or char, or in the air pollution control equipment. This research focuses on identifying the rate-limiting steps associated with the oxidation step. Work in this reporting period focused on the refinement of the rate constants used in the kinetic mechanism for mercury oxidation. The possible reactions leading to mercury oxidation are reviewed. Rate constants for these reactions are discussed, using both literature sources and detailed estimates. The resulting mechanism represents the best present picture of the overall chlorine homogeneous oxidation chemistry. Application of this mechanism to the data will be explored in the subsequent reporting period. Work conducted under the present grant has been the subject of two meeting papers presented during the reporting period (Sliger et al., 1998a,b).
Date: August 6, 1999
Creator: Kramlich, John C.; Sliger, Rebecca N. & Going, David J.
Partner: UNT Libraries Government Documents Department

REDUCTION OF INHERENT MERCURY EMISSIONS IN PC COMBUSTION

Description: Mercury emission compliance is one of the major potential challenges raised by the 1990 Clean Air Act Amendments. Simple ways of controlling emissions have not been identified. The variability in the field data suggests that inherent mercury emissions may be reduced if the source of this inherent capture can be identified and controlled. The key mechanisms appear to involve the oxidation of the mercury to Hg{sup 2}, generally producing the more reactive HgCl{sub 2}, followed by its capture by certain components of the fly ash or char. This research focuses on identifying the rate-limiting steps associated with the oxidation step. Work in this reporting period focused on the development of oxidation data as a function of temperature and HCl concentration. The temperature range was 800-1200 C. The results show a lower level of oxidation than indicated by the earlier data of Hall et al. (1991). One possible reason for this discrepancy was the preheating of the HCl stream in the Hall experiment, leading to the partial decomposition of the HCl into reactive species. In the present experiments, the HCl was injected as a cold stream. The measured oxidation at these conditions was substantially above that predicted by equilibrium, indicating the dominance of finite rate chemistry. This is to be explored in subsequent work.
Date: August 19, 1998
Creator: Kramlich, John C.; Sliger, Rebecca N. & Going, David J.
Partner: UNT Libraries Government Documents Department

REDUCTION OF INHERENT MERCURY EMISSIONS IN PC COMBUSTION

Description: Mercury emission compliance presents one of the major potential challenges raised by the 1990 Clean Air Act Amendments. Simple ways of controlling emissions have not been identified. The variability in the field data suggest that inherent mercury emissions may be reduced if the source of this inherent capture can be identified and controlled. The key mechanisms appear to involve the oxidation of mercury to Hg{sup 2}, generally producing the more reactive HgCl{sub 2}, followed by its capture by certain components of the fly ash or char, or in the air pollution control equipment. This research focuses on identifying the rate-limiting steps associated with the oxidation step. Work in this reporting period focused on testing of the kinetic mechanism reported in the previous semiannual report, and the interpretation of data (both ours and literature). This model yields good qualitative agreement with the data and indicates that mercury oxidation occurs during the thermal quench of the combustion gases. The model also suggests that atomic chlorine is the key oxidizing species. The oxidation is limited to a temperature window between 700-400 C that is defined by the overlap of (1) a region of significant superequilibrium Cl concentration, and (2) a region where oxidized mercury is favored by equilibrium. Above 700 C reverse reactions effectively limit oxidized mercury concentrations. Below 400 C, atomic chlorine concentrations are too low to support further oxidation. The implication of these results are that homogeneous oxidation is governed primarily by (1) HCl concentration, (2) quench rate, and (3) background gas composition. Work conducted under the present grant has been the subject of one journal paper that was accepted for publication during the reporting period (Sliger et al., 1999).
Date: August 6, 1999
Creator: Kramlich, John C.; Sliger, Rebecca N. & Going, David J.
Partner: UNT Libraries Government Documents Department

Mercury extraction by the TRUEX process solvent: I. Kinetics, extractable species, dependence on nitric acid concentration and stoichiometry

Description: Mercury extraction from acidic aqueous solutions by the TRUEX process solvent (0.2 M CMPO, 1.4 M TBP in n-dodecane) has not extensively been examined. Research at the Idaho Chemical Processing Plant is currently in progress to evaluate the TRUEX process for actinide removal from several acidic waste streams, including liquid sodium-bearing waste (SBW), which contains significant quantities of mercury. Preliminary experiments were performed involving the extraction of Hg{sup 203}, added as HgCl{sub 2}, from 0.01 to 10 M HNO{sub 3} solutions. Mercury distribution coefficients (D{sub Hg}) range between 3 and 60 from 0.01 M to 2 M HNO{sub 3}. At higher nitric acid concentrations, i.e. 5 M HNO{sub 3} or greater, D{sub Hg} significantly decreases to values less than 1. These results indicate mercury is extracted from acidic solutions {<=}{approximately}2 M HNO{sub 3} and stripped with nitric acid solutions {>=}{approximately}5 M HNO{sub 3}. Experimental results indicate the extractable species is HgCl{sub 2} from nitrate media, i.e., chloride must be present in the nitrate feed to extract mercury. Extractions from Hg(NO{sub 3}){sub 2} solutions indicated substantially reduced distribution ratios, typically D{sub Hg}< 1, for the range of nitric acid concentrations examined (0.01 to 8 M HNO{sub 3}). Extraction of mercury, as HgCl{sub 2}, by the individual components of the TRUEX solvent was also examined from 2 M HNO{sub 3}. The diluent, n-dodecane, does not measurably extract mercury. With a 1.4 M TBP/n-dodecane solvent, D{sub Hg} {approximately}3.4 compared with D{sub Hg} {approximately}7 for the TRUEX solvent. Classical slope analysis techniques were utilized to evaluate the stoichiometric coefficients of Hg extraction independently for both CMPO and TBP.
Date: December 1, 1995
Creator: Herbst, R.S.; Brewer, K.N.; Tranter, T.J. & Todd, T.A.
Partner: UNT Libraries Government Documents Department

Portable sensor for hazardous waste

Description: Objective was to develop a field-portable monitor for sensitive hazardous waste detection using active nitrogen energy transfer (ANET) excitation of atomic and molecular fluorescence (active nitrogen is made in a dielectric-barrier discharge in nitrogen). It should provide rapid field screening of hazardous waste sites to map areas of greatest contamination. Results indicate that ANET is very sensitive for monitoring heavy metals (Hg, Se) and hydrocarbons; furthermore, chlorinated hydrocarbons can be distinguished from nonchlorinated ones. Sensitivity is at ppB levels for sampling in air. ANET appears ideal for on-line monitoring of toxic heavy metal levels at building sites, hazardous waste land fills, in combustor flues, and of chlorinated hydrocarbon levels at building sites and hazardous waste dumps.
Date: December 31, 1994
Creator: Piper, L.G.
Partner: UNT Libraries Government Documents Department

MODELING THE IMPACT OF ELEVATED MERCURY IN DEFENSE WASTE PROCESSING FACILITY MELTER FEED ON THE MELTER OFF-GAS SYSTEM - PRELIMINARY REPORT

Description: The Defense Waste Processing Facility (DWPF) is currently evaluating an alternative Chemical Process Cell (CPC) flowsheet to increase throughput. It includes removal of the steam-stripping step, which would significantly reduce the CPC processing time and lessen the sampling needs. However, its downside would be to send 100% of the mercury that come in with the sludge straight to the melter. For example, the new mercury content in the Sludge Batch 5 (SB5) melter feed is projected to be 25 times higher than that in the SB4 with nominal steam stripping of mercury. This task was initiated to study the impact of the worst-case scenario of zero-mercury-removal in the CPC on the DWPF melter off-gas system. It is stressed that this study is intended to be scoping in nature, so the results presented in this report are preliminary. In order to study the impact of elevated mercury levels in the feed, it is necessary to be able to predict how mercury would speciate in the melter exhaust under varying melter operating conditions. A homogeneous gas-phase oxidation model of mercury by chloride was developed to do just that. The model contains two critical parameters pertaining to the partitioning of chloride among HCl, Cl, Cl{sub 2}, and chloride salts in the melter vapor space. The values for these parameters were determined at two different melter vapor space temperatures by matching the calculated molar ratio of HgCl (or Hg{sub 2}Cl{sub 2}) to HgCl{sub 2} with those measured during the Experimental-Scale Ceramic Melter (ESCM) tests run at the Pacific Northwest National Laboratory (PNNL). The calibrated model was then applied to the SB5 simulant used in the earlier flowsheet study with an assumed mercury stripping efficiency of zero; the molar ratio of Cl-to-Hg in the resulting melter feed was only 0.4, compared to 12 for the ...
Date: March 25, 2009
Creator: Zamecnik, J. & Choi, A.
Partner: UNT Libraries Government Documents Department

REDUCTION OF INHERENT MERCURY EMISSIONS IN PC COMBUSTION

Description: Mercury emission compliance is one of the major potential challenges raised by the 1990 Clean Air Act Amendments. Simple ways of controlling emissions have not been identified. The variability in the field data suggests that inherent mercury emissions may be reduced if the source of this inherent capture can be identified and controlled. The key mechanisms appear to involve the oxidation of the mercury to Hg{sup 2}, generally producing the more reactive HgCl{sub 2} , followed by its capture by certain components of the fly ash or char. This research focuses on identifying the rate-limiting steps associated with the oxidation step. Work in this reporting period focused on the development and application of a kinetics model to the oxidation data developed in the present program and literature data under MSW conditions. The results indicate that the pathway Hg + Cl = HgCl followed by HgCl + HCl = HgCl{sub 2} + H predominates over Hg + Cl{sub 2} under high-temperature conditions. This primarily occurs because Cl{sub 2} concentrations are too low under the present conditions to contribute significantly.
Date: August 6, 1999
Creator: Kramlich, John C.; Sliger, Rebecca N. & Going, David J.
Partner: UNT Libraries Government Documents Department

Reactions of gaseous, elemental mercury with dilute halogen solutions

Description: Of the trace elements known to exist in fossil fuels, mercury (Hg) has emerged as one of the greatest concerns. Mercury has been found to be emitted from combustion in at least two different chemical forms: elemental Hg and oxidized Hg compounds. Precise identification of the oxidized compounds emitted has not been accomplished to date. However, most workers in this field assume that mercuric chloride should be the predominant oxidized species. Mercuric chloride should be readily removed in a wet scrubber system because of its relatively high solubility in water. However, it has been presumed, and we have shown, that elemental Hg will pass through a wet scrubber system with little or no removal being effected. Therefore, it is important, in order to obtain a high total Hg removal, to study methods that might result in a removal of gaseous, elemental Hg from a flue-gas stream. In this regard, we have been studying the effect of dilute halogen-containing solutions on elemental Hg in gas streams of various compositions. In particular, the results of passing Hg through bubblers containing solutions of iodine, chlorine, and chloric acid are described. Mercury found in the bubbler solutions is an indication of the extent of reaction (oxidation) of elemental Hg with the halogen species, since we have found very little Hg transferred to the liquid phase when only distilled water is used in the bubblers. Results using commercial iodine, sodium hypochlorite, and NOXSORB (sup TM) solutions are presented and discussed.
Date: July 1996
Creator: Mendelsohn, M. H. & Livengood, C. D.
Partner: UNT Libraries Government Documents Department

MODELING THE IMPACT OF ELEVATED MERCURY IN DEFENSE WASTE PROCESSING FACILITY MELTER FEED ON THE MELTER OFF-GAS SYSTEM-PRELIMINARY REPORT

Description: The Defense Waste Processing Facility (DWPF) is currently evaluating an alternative Chemical Process Cell (CPC) flowsheet to increase throughput. It includes removal of the steam-stripping step, which would significantly reduce the CPC processing time and lessen the sampling needs. However, its downside would be to send 100% of the mercury that comes in with the sludge straight to the melter. For example, the new mercury content in the Sludge Batch 5 (SB5) melter feed is projected to be 25 times higher than that in the SB4 with nominal steam stripping of mercury. This task was initiated to study the impact of the worst-case scenario of zero-mercury-removal in the CPC on the DWPF melter offgas system. It is stressed that this study is intended to be scoping in nature, so the results presented in this report are preliminary. In order to study the impact of elevated mercury levels in the feed, it is necessary to be able to predict how mercury would speciate in the melter exhaust under varying melter operating conditions. A homogeneous gas-phase oxidation model of mercury by chloride was developed to do just that. The model contains two critical parameters pertaining to the partitioning of chloride among HCl, Cl, Cl{sub 2}, and chloride salts in the melter vapor space. The values for these parameters were determined at two different melter vapor space temperatures by matching the calculated molar ratio of HgCl (or Hg{sub 2}Cl{sub 2}) to HgCl{sub 2} with those measured during the Experimental-Scale Ceramic Melter (ESCM) tests run at the Pacific Northwest National Laboratory (PNNL). The calibrated model was then applied to the SB5 simulant used in the earlier flowsheet study with an assumed mercury stripping efficiency of zero; the molar ratio of Cl-to-Hg in the resulting melter feed was only 0.4, compared to 12 for the ...
Date: August 18, 2010
Creator: Zamecnik, J. & Choi, A.
Partner: UNT Libraries Government Documents Department

CONTINUOUS DISSOLUTION OF ZIRCONIUM REACTOR FUELS IN TITANIUM EQUIPMENT: LABORATORY DEMONSTRATION

Description: Continuous dissolution of 2% U-- Zr alloy fuel in a laboratory-scale Ti dissolver was demonstrated using refluxing 3 M HNO/sub 3/--1.2 M HF--0.4 M HBF/ sub 4/--0.6 M Cr(III)0.4 M Cr(VI)--0.46 M Zr as the dissolvent. Dissolution rates and solution corrosion rates were 8 to 16 mg/cm/sup 2/min and approximates 1 mil/month, respectively. Reagent was added to the dissolver at the rate needed to maintain the potential measured by a Au vs. calomel electrode in the product effluent as close to a preselected standard value as possible. (auth)
Date: January 23, 1963
Creator: Gens, T.A.
Partner: UNT Libraries Government Documents Department

Recovery and removal of mercury from mixed wastes. Final report, September 1994--June 1995

Description: In recognition of the major environmental problem created by mercury contamination of wastes and soils at an estimated 200,000 sites along US natural gas and oil pipelines and at a number of government facilities, including Oak Ridge, Savannah River, Hanford, and Rocky Flats, the US Department of Energy (DOE) is seeking an effective and economical process for removing mercury from various DOE waste streams in order to allow the base waste streams to be treated by means of conventional technologies. In response to the need for Unproved mercury decontamination technology, Mercury Recovery Services (MRS) has developed and commercialized a thermal treatment process for the recovery of mercury from contaminated soils and industrial wastes. The objectives of this program were to: demonstrate the technical and economic feasibility of the MRS process to successfully remove and recover mercury from low-level mixed waste containing mercury compounds (HgO, HgS, HgCl{sub 2}) and selected heavy metal compounds (PbO, CdO); determine optimum processing conditions required to consistently reduce the residual total mercury content to 1 mg/kg while rendering the treated product nontoxic as determined by TCLP methods; and provide an accurate estimate of the capital and operating costs for a commercial processing facility designed specifically to remove and recovery mercury from various waste streams of interest at DOE facilities. These objectives were achieved in a four-stage demonstration program described within with results.
Date: June 1, 1995
Creator: Sutton, W.F.; Weyand, T.E. & Koshinski, C.J.
Partner: UNT Libraries Government Documents Department

Excitation and dissociation mechanisms in molecules with application to mercuric halide laser system

Description: Although the mercuric halide laser systems have received intensive study in recent years, being one of only two efficient electronic-transition lasers known, the precise collisional mechanisms leding to HgBr(B), formation and subsequent fluorescence are still imperfectly understood. The initial suggestion that direct collisional excitation of, say, HgBr/sub 2/, by electrons (analogous to photoionization), i.e., HgBr/sub 2/ + e ..-->.. HgBr(b) + Br + e, was the dominant mechanism, was temporarily abandoned when a measurement by Allison and Zare yielded a cross section of only < 1 x 10/sup -20/ cm/sup 2/ for low incident electron energy HgBr(B-x) fluorescence, much too small to explain the observed laser efficiency. Subsequent explanations for HgBr(B) formation included energy transfer from excited N/sub 2/ or rare gases, electronic recombination of HgBr/sub 2//sup +/, or dissociative electron attachment. Though it has recently been demonstrated that electronic energy transfer does play a role in HgBr(B) formation in the presence of N/sub 2/ or X/sub e/ buffers, modeling studies of e-beam sustained discharges have now conclusively shown that direct electron-impact excitation of mercuric halides, is indeed the dominant laser mechanism. The technique of electron-energy-loss spectroscopy was used to obtain pseudo-optical absorption spectra in HgBr/sub 2/ and HgCl/sub 2/. Results are presented and discussed. (WHK)
Date: January 1, 1982
Creator: Spence, D.; Wang, R.G. & Dillon, M.A.
Partner: UNT Libraries Government Documents Department