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At least 685 records · Page 38

Reactive-transport modeling of fracture flow to quantify the changes in flow pathways from matrix thermal contraction and mineral precipitation and dissolution; influence of grid resolution

A series of reactive-transport models of Enhanced Geothermal Systems (EGS) were constructed using the reactive transport code PFLOTRAN to examine the effect of matrix thermal contraction and mineral dissolution/precipitation on fracture flow in the context of grid cell size and model complexity. It was found that for thermal drawdown at production well, the impact of fracture zone grid cell size is negligible.

Gatz-Miller, Hannah Sarah↗

FY24 Task 4: Studies of Phosphate and Fluoride Solubility for Dissolution of High Phosphate Tank Waste

Knowledge gaps have been identified in phosphate solubility in almost every single- and multi-component system, and particularly for aluminate in phosphate/hydroxide, where uncertainties in predicted values of aluminum solubility are greater than 50%. Solubility data of multicomponent, aqueous electrolytes containing sodium hydroxide, sodium fluoride, sodium phosphate, sodium nitrite, sodium nitrate, and dissolved gibbsite are also sparse. For example, for solutions of (i) sodium nitrate and sodium phosphate, data are only available at 30 and 50 °C, and for (ii) dissolved gibbsite in sodium hydroxide and sodium phosphate, only two data points are available at 20 and 40 °C. There is no data available on mixtures of sodium hydroxide, sodium phosphate, sodium fluoride, and dissolved gibbsite. These knowledge gaps were identified in a technical review of waste solubility data and the impact of dilution on solution stabilities and will be addressed in this work to predict aluminum hydroxide and sodium phosphate solubility in multicomponent electrolytes upon dilution, and upon variation of temperature. Results will provide the technical basis to develop accurate models for (i) gibbsite solubility and mass transfer of aluminum between solid and liquid forms following the sluicing of sludge and saltcake with water; and (ii) further blending of these suspensions with bismuth from bismuth phosphate waste, and zirconium and uranium left from the fuel decladding. This work will be essential to developing a disposition path for retrieval solutions from bismuth phosphate wastes. This effort would also support sludge washing to further reduce phosphate concentration if that process were to be added back to the flowsheet in the future.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of Leaf Water Potential on Internal Humidity and CO 2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flat surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO 2 , thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO 2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Here, our results indicate that the reduction in vapor pressures of water and CO 2 could enhance plant water use efficiency up to about 10% at a leaf water potential of -2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. Lastly, the omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO 2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.

54 ENVIRONMENTAL SCIENCES↗

Extremely high-rate, uniform dissolution of alloy C-22 in anhydrous organic solutions at room temperature

During routine pharmaceutical development and scale-up work, severe corrosion of a Hastelloy Alloy C-22 filter dryer was observed after single, short (several hours) contact with the product slurry at room temperature. Initial investigations showed that the presence of both 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HCl was sufficient in an acetonitrile solution to cause rapid corrosion of C-22. More detailed mass loss studies showed initial corrosion rates exceeding25 mm/year that then decreased over several hours to steady state rates of 3-5 mm/year. The corrosion was highly uniform. Electrochemical measurements demonstrated that although C-22 is spontaneously passive in acetonitrile solution, the presence of HCl leads to the development of a transpassive region. Furthermore, DDQ is a sufficiently strong oxidizer, particularly in acidic solutions, to polarize the C-22 well into the transpassive region, leading to the observed high corrosion rates.

36 MATERIALS SCIENCE↗

Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

Stecura, S.↗