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At least 487 records · Page 27

Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

Iraci, L. T.↗

Dissolution and reduction of magnetite by bacteria

Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis.

Non-NASA Center↗

Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite

Beiersdorfer, R. E.↗

Dissolution of Olivine, Siderite, and Basalt at 80 Deg C in 0.1 M H2SO4 in a Flow Through Process: Insights into Acidic Weathering on Mars

The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

Golden, D. C.↗

Silica Dissolution and Precipitation in Galciated Volcanic Environments and Implications for Mars

The surface of Mars exhibits strong evidence for a widespread and long-lived cryosphere. Observations of the surface have identified phases produced by water-rock interactions, but the contribution of glaciers to the observed alteration mineralogy is unclear. To characterize the chemical alteration expected on an icy early Mars, we collected water and rock samples from terrestrial glaciated volcanics. We related geochemical measurements of meltwater to the mineralogy and chemistry of proglacial rock coatings. In these terrains, water is dominated by dissolved silica relative to other dissolved cations, particularly at mafic sites. Rock coatings associated with glacial striations on mafic boulders include a silica-rich component, indicating that silica precipitation is occurring in the subglacial environment. We propose that glacial alteration of volcanic bedrock is dominated by a combination of high rates of silica dissolution and precipitation of opaline silica. On Mars, cryosphere-driven chemical weathering could be the origin of observed silica-enriched phases.

Rutledge, A. M.↗

Safe Dissolution of High Flux Isotope Reactor Cores

The H-Canyon facility at the Savannah River Site is the U.S.A.’s only remaining full- scale chemical separations plant. H-Canyon maintains the capacity to safely and efficiently disposition a large inventory of excess nuclear material from across the Department of Energy (DOE) complex and used nuclear fuel from foreign and domestic research reactors. One such fuel that H-Canyon may dissolve is cores from the High Flux Isotope Reactor (HFIR). By employing realistic analysis, the need for administrative controls was eliminated. A new criticality modeling approach has eliminated the need for administrative controls for HFIR dissolution operations in H-Canyon. The primary upsets of concern are an over-mass event and an overconcentration event. Several initiating events were considered for each type of upset. Over-concentration events were deemed to be not credible by taking credit for the chemistry of acid consumption, i.e. there are not enough moles of acid to dissolve enough moles of uranium in order to reach a critical configuration. Over-mass events were deemed to be not credible by taking credit for the annular design of the fuel elements. By using realistic analysis, both types of upsets have been shown to be subcritical, and therefore administrative controls are not needed to prevent an inadvertent criticality. In this paper, the new methodology for performing criticality analyses for dissolving HFIR fuel elements will be presented, and the elimination of administrative controls will be discussed.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

System and process for dissolution of solids

A system and process are disclosed for dissolution of solids and "difficult-to-dissolve" solids. A solid sample may be ablated in an ablation device to generate nanoscale particles. Nanoparticles may then swept into a coupled plasma device operating at atmospheric pressure where the solid nanoparticles are atomized. The plasma exhaust may be delivered directly into an aqueous fluid to form a solution containing the atomized and dissolved solids. The composition of the resulting solution reflects the composition of the original solid sample.

36 MATERIALS SCIENCE↗

Dissolution and separation of rare earth metals

A chemical dissolution method is provided for use in recycling rare earth metal-containing material such as permanent magnet material including end-of-life magnet shapes, magnet scrap and Terfenol-D alloy material by mixing the rare earth metal-containing material and an aqueous solution of a copper (II) salt to dissolve the material in the solution. The dissolved rare earth metal is then precipitated from the aqueous solution as a rare earth metal compound, such as a rare earth metal oxalate, sulfate or phosphate from which rare earth metal oxide can be obtained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dissolution of Mechanically Mixed UO2-PuO2 and Insoluble Residue Characteristics

During the reprocessing operations of mixed oxide fuel the dissolution step plays a very important role in the attainment of an acceptable plutonium recovery yield. The importance of this step on the overall fuel cycle was recognized by many authors but was especially treated in depth by Lerch [1] and Nicholson [2].

De Regge, P.↗

Evaluation of the Effects of Microbes on Autunite Dissolution and the Spectral Induced Polarization Response in Hanford Vadose Zone Sediment - 18440

As a result of the U.S. nuclear weapons program during the second World War and throughout the Cold War, there now exists a significant amount of uranium contamination at the U.S. Department of Energy Hanford site located in Washington State. Much of this contamination is in the form of mobile uranyl carbonates species within the vadose zone, which at Hanford varies up to 100 m thick in the Central Plateau. In-situ immobilization of mobile uranium via injections of a soluble sodium tripolyphosphate amendment may prove effective in the formation of low-solubility uranyl phosphate solid phases, autunite. However, the injected polyphosphate undergoes hydrolysis in aqueous solutions to form orthophosphate, which serves as a readily available nutrient for the various microorganisms in the sediment. Sediment-filled column experiments conducted under saturated oxygen restricted conditions using a geophysical technique known as spectral induced polarization (SIP) have shown the impact of microbes on the dissolution of synthetic autunite. Two sets of experiments were conducted using test columns. Each experiment had a pair of columns inoculated with microbes (with a glucose solution acting as a nutrient source) which were monitored using SIP in conjunction with regular sampling of pore-water. Columns were built with two silver/silver chloride (Ag/AgCl) coiled current electrodes at either end and four Ag potential electrodes along the side, which allowed the measurement of three distinct points along the length of the column. SIP measures phase which is the time delay between an injected current and measured voltage, in this case measured in radians. Three sampling ports were added to correspond with the geophysical measurements. Pore-water samples taken over the course of the experiment were analyzed for dissolved elements including uranium, iron, phosphorous, calcium, and magnesium. SIP results were plotted over time in order to determine correlations between changes in electrical phase and changes in pore-water chemistry. It was determined that changes in the phase and bulk resistivity detected with SIP corresponded to changes in the pore-water chemistry due to the growth of microbes. The first experiment ran for five months and had measurements done once a week, the second only ran one month but had measurements taken five times a week in order to understand initial changes in column chemistry in greater detail. SIP may be an effective way to remotely track changes indicative of bacterial activities on the surrounding environment. This method has the potential for field application at a larger scale for the purpose of tracking microbe growth in response to tripolyphosphate amendment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Fluid Flow, Dissolution, and Mixing Phenomena in Argon-Stirred Steel Ladles

In the current study, the multiphase fluid flow in argon-stirred steel ladles is simulated using an Eulerian–Lagrangian two-phase approach. The momentum source and the turbulent kinetic energy source due to the motion of the bubble are considered for the liquid phase. Argon bubbles are treated as discrete phase particles, and the interfacial forces between the bubbles and the liquid phase; the dependence of the gas density and the bubble diameter on the temperature and the static pressure; and the bubble size distribution are considered. When the fluid flow reaches the quasi-steady state, the ferroalloy melting and mixing phenomena is also modeled. The melting time and the trajectory length of each ferroalloy particle are recorded using a user-defined function (UDF). Local mixing time is predicted in the entire computational domain by checking the mixing criteria in every cell. The effects of gas flow rate, porous plug location, and separation angle of two porous plugs on the fluid flow and the mixing phenomena are investigated. The results show that the flow intensity increases, and the mixing time decreases with the increasing gas flow rate. The optimal porous plug’s radial position with one porous plug is 0.50R for its best mixing condition. When two porous plugs are adopted, the separation angle of 90 deg is recommended to improve the flow field and mixing phenomena.

42 ENGINEERING↗

Impact of initial CA dissolution on the hydration mechanism of CAC

Usually, for basic investigations on the hydration behaviour of CA (monocalcium aluminate, CaAl{sub 2}O{sub 4}) preferably pure samples without the presence of other hydraulic phases are used. In the presented study we apply an alternative approach investigating mixes that contain tiny to low amounts of CA (0.5–20 wt%) besides CA{sub 2} (CaAl{sub 4}O{sub 7}) or C{sub 6}AF{sub 2} (Ca{sub 6}Al{sub 2}Fe{sub 4}O{sub 15}). The hydration of the mixes is investigated by isothermal heat flow calorimetry, in-situ XRD and pore solution analysis at 23 °C. A modified thermodynamic database enables the calculation of saturation indices for relevant hydrate phases in the investigated systems. CA similarly influences the hydration of both CA{sub 2} and C{sub 6}AF{sub 2} although the exact impact strongly depends on the initial CA/water ratio in the mixes. Up to a certain amount CA is completely consumed during the first minutes after mixing. Beyond this amount the presence of undissolved CA causes an induction period and retards the hydration of CA{sub 2} or C{sub 6}AF{sub 2}.

36 MATERIALS SCIENCE↗