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At least 325 records · Page 18

On the Goertler instability in hypersonic flows: Sutherland law fluids and real gas effects

The Goertler vortex instability mechanism in a hypersonic boundary layer on a curved wall is investigated. The precise roles of the effects of boundary layer growth, wall cooling, and gas dissociation is clarified in the determination of stability properties. It is first assumed that the fluid is an ideal gas with viscosity given by Sutherland's law. It is shown that when the free stream Mach number M is large, the boundary layer divides into two sublayers: a wall layer of O(M sup 3/2) thickness over which the basic state temperature is O(M squared) and a temperature adjustment layer of O(1) thickness over which the basic state temperature decreases monotonically to its free stream value. Goertler vortices which have wavelengths comparable with the boundary layer thickness are referred to as wall modes. It is shown that their downstream evolution is governed by a set of parabolic partial differential equations and that they have the usual features of Goertler vortices in incompressible boundary layers. As the local wavenumber increases, the neutral Goertler number decreases and the center of vortex activity moves towards the temperature adjustment layer. Goertler vortices with wavenumbers of order one or larger must necessarily be trapped in the temperature adjustment layer and it is this mode which is most dangerous. For this mode, it was found that the leading order term in the Goertler number expansion is independent of the wavenumber and is due to the curvature of the basic state. This term is also the asymptotic limit of the neutral Goertler numbers of the wall mode. To determine the higher order corrections terms in the Goertler number expansion, two wall curvature cases are distinguished. Real gas effects were investigated by assuming that the fluid is an ideal dissociating gas. It was found that both gas dissociation and wall cooling are destabilizing for the mode trapped in the temperature adjustment layer, but for the wall mode trapped near the wall the effect of gas dissociation can be either destabilizing or stabilizing.

Fu, Yibin B.↗

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)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst

Dry reforming of methane (DRM) is a process that converts two greenhouse gases (methane and carbon dioxide) into syngas, a mixture of H 2 and CO, that can lead to a variety of value-added chemicals. Owing to its endothermic nature, high reaction temperatures up to 800 °C are typically required and the grand challenge lies in developing robust catalysts without sintering and coking-induced deactivation during the long-term on-stream operation. Towards this aim, herein, a robust complex oxide-supported NiCu alloy catalyst was generated in situ during DRM. By leveraging the configurational stability of a solid oxide solution precursor, tightly anchored NiCu bimetallic nanoparticles were in situ exsoluted and acted as the active sites in DRM. The as-afforded catalyst exhibited stable performance for DRM due to the ability to repel coke off the surface as the reaction proceeds. Kinetic experiments along with top surface characterization detail the reconstruction behavior of the solid oxide solution under DRM reaction conditions. In conclusion, the fundamental insights from this work provide guidance on generating resistant and flexible catalysts via in situ active sites formation from easily synthesized metal oxide solid solutions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Single Crystal Optical Fiber and Perovskite Oxide Sensing Materials for Gas Monitoring above 500 °C

A wide range of high-value applications, including power generation and chemical manufacturing, involve harsh chemical conditions and extreme temperatures. In this work, we discuss the pairing of single crystal optical fiber with optically responsive, high-temperature stable perovskite oxide materials for monitoring of oxidizing and reduction gas streams up to 1000 °C. Optical sensing will be presented for hydrogen and oxygen monitoring in this temperature regime. Strategies will be discussed for improving stability and eliminating drift via multi-wavelength detection. The application of spatially resolved interrogation techniques, such as optical time domain reflectometry (OTDR) will be addressed for these sensors.

Wuenschell, Jeffrey↗

Results of an investigation of hypersonic viscous interaction effects of the space shuttle orbiter using a 0.010 scale model (51-0) in the AEDC-VKF tunnel F (OA160)

An experimental aerodynamic investigation was conducted in the AEDC-VKF Hypervelocity Wind Tunnel (Tunnel F) at a nomial Mach number of 19 to determine hypersonic viscous interaction effects on the space shuttle orbiter. The tests were conducted at an angle of attack of 30 degrees over a free-stream Reynolds number (based on fuselage length) variation from 0.1 to 0.4 million. Viscous interaction parameter was varied from 0.02 to 0.06. Six component static stability force and moment data were measured by an internally compensated internal strain gage balance. Resulting data are presented.

Elder, D. J.↗

Enhanced alkaline hydrolysis and biodegradability studies of nitrocellulose-bearing missile propellant

Large amounts of energetic materials which have been accumulated over the years in various manufacturing and military installations must be disposed of in an environmentally sound manner. Historically, the method of choice for destruction of obsolete or aging energetic materials has been open burning or open detonation (OB/OD). This destruction approach has become undesirable due to air pollution problems. Therefore, there is a need for new technologies which will effectively and economically deal with the disposal of energetic materials. Along those lines, we have investigated a chemical/biological process for the safe destruction and disposal of a double base solid rocket propellant (AHH), which was used in several 8 inch projectile systems. The solid propellant is made of nitrocellulose and nitroglycerin as energetic components, two lead salts which act as ballistic modifiers, triacetin as a plasticizer and 2-Nitrodiphenylamine (2-NDPA) as a stabilizer. A process train is being developed to convert the organic components of the propellant to biodegradable products and remove the lead from the process stream. The solid propellant is first hydrolyzed through an enhanced alkaline hydrolysis process step. Following lead removal and neutralization, the digested liquor rich in nitrates and nitrites is found to be easily biodegradable. The digestion rate of the intact ground propellant as well as the release of nitrite and nitrate groups were substantially increased when ultrasound were supplied to the alkaline reaction medium compared to the conventional alkaline hydrolysis. The effects of reaction time, temperature, sodium hydroxide concentration and other relevant parameters on the digestion efficiency and biodegradability have been studied. The present work indicates that the AHH propellant can be disposed of safely with a combination of physiochemical and biological processes.

Sidhoum, Mohammed↗

Flutter Sensitivity to Boundary Layer Thickness, Structural Damping, and Static Pressure Differential for a Shuttle Tile Overlay Repair Concept

This paper examines the aeroelastic stability of an on-orbit installable Space Shuttle patch panel. CFD flutter solutions were obtained for thick and thin boundary layers at a free stream Mach number of 2.0 and several Mach numbers near sonic speed. The effect of structural damping on these flutter solutions was also examined, and the effect of structural nonlinearities associated with in-plane forces in the panel was considered on the worst case linear flutter solution. The results of the study indicated that adequate flutter margins exist for the panel at the Mach numbers examined. The addition of structural damping improved flutter margins as did the inclusion of nonlinear effects associated with a static pressure difference across the panel.

Scott, Robert C.↗

High-Temperature Ceramic-Carbonate Dual-Phase Membrane Reactor for Pre-combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Arizona State University, in collaboration with University of South Carolina, worked on a project aimed at development of a new high temperature, high pressure CO 2 perm-selective membrane reactor for water-gas-shift reaction (WGS) with simulated gasifier syngas to produce a high concentration H 2 stream with CO 2 capture. The membrane reactor is made of a CO 2 semi-permeable ceramic-carbonate dual-phase (CCDP) membrane with high CO 2 perm-selectivity/permeance and thermal/mechanical stability for application in WGS reaction. The objectives of this project were to (1) synthesize the chemically/thermally stable tubular CCDP membranes with CO 2 permeance and selectivity (with respect to H 2 , CO or H 2 O) larger than 6.5×10-7 mol/m2·s·Pa and 500, respectively; (2) establish CCDP membrane reactor setup and study high pressure CO 2 permeation and WGS reaction with CO 2 capture using the setup; and (3) identify conditions for WGS in the CCDP membrane reactor that produce CO 2 and H 2 streams with purity of >99% and >90% respectively at CO conversion >95% and overall carbon capture >90%. The work in this project included both membrane development and membrane reactor process study. The membrane development efforts were focused on investigating a H 2 S resistant and highly oxygen-ionic conducting metal oxide material and membrane for CO 2 separation, fabrication of tubular samaria-doped-ceria/molten-carbonate CCDP membrane with high mechanical strength, and experimental and modeling study of high-pressure CO 2 permeation of the CCDP membranes. Mathematical models were developed to describe WGS in the CCDP membrane reactor without a catalyst or packed with a commercial high temperature WGS catalyst. Experiments on WGS in the CCDP membrane reactor with the commercial WGS catalyst, guided by the model analysis, were performed to identify optimum conditions for achieving the CO conversion, carbon capture, and the purity of the H 2 and CO 2 streams mentioned above. At 30 atm feed pressure, 750°C operation temperature, space velocity of 250 h-1, and with steam sweep, a single-stage CCDP membrane reactor with average CO 2 permeation flux of 0.5 cm3(STP)/min.cm2 can achieve CO 2 conversion of 95% and overall carbon capture of 94%, and produce CO 2 and H 2 streams with dry-based purity of >99% and 92% respectively. The project also included process design and techno-economic analysis (TEA) for a CCDP membrane reactor process for WGS reaction with CO 2 capture for a 550 MW coal-fired IGCC power plant, and its comparison with the conventional fixed-bed reactor system for WGS with follow-up CO 2 capture by an amine absorption process. The target performance for the reactor for WGS with CO 2 capture includes CO conversion >95%, hydrogen stream purity >90%, CO 2 stream purity >95%, and total carbon capture >90%. The CCDP membrane developed in this project can achieve the performance target, without subsequent CO 2 capture process at the optimum conditions identified in this project. The outcome of the process design and TEA analysis shows that the membrane reactor for WGS with in-situ CO 2 capture has an operating cost about 40% lower than that for the conventional fixed-bed reactor with a separate amine absorption process for CO 2 capture. However, the capital cost of the membrane reactor process is about twice that of the conventional process because of the higher cost of the CCDP membrane. Modeling analysis shows that a membrane reactor using a CCDP membrane with higher CO 2 permeance (about three times the current value) can deliver the targeted performance for WGS reaction with CO 2 capture at a much higher space velocity and lower membrane surface area to catalyst volume ratio, leading to a smaller catalyst amount and/or membrane area and hence significantly reduced membrane reactor capital costs.

20 FOSSIL-FUELED POWER PLANTS↗

Effect of combined pressure and temperature distortion orientation on high-bypass-ratio turbofan engine stability

Total-temperature, static-pressure and total-pressure distributions were measured in the inlet duct upstream of the engine inlet and within the fan and compressor of a YTF34 turbofan engine. Free-stream and boundary layer yaw angle variations were measured between a rotable screen assembly and the engine inlet. Total pressure distortions were generated using three 180 deg extent screens and total temperature distortions were generated using a rotatable hydrogen burner. Reynolds number index upstream of the rotatable screen assembly was maintained at 0.5 (based on the undistorted sectors at station 1, the inlet flow measuring station). The engine mechanical fan speed at sea level condition was rated at 7005 rpm. The engine was tested at a corrected fan speed of 90 percent of rated condition. Yaw angle increased between the rotatable screen assembly and the engine inlet. The largest variation in free-stream and boundary layer yaw angle occurs when the combined distortions are 180 deg out-of-phase. Static-pressure distortion increased exponentially as flow approached the engine. Total-pressure distortions were attenuated between the engine inlet and the compressor exit. Total-temperature distortion persisted through the compressor for all four combined distortions investigated.

Soeder, R. H.↗

Understanding and tuning organocatalysts for versatile condensation polymer deconstruction

Plastics are widely used for their durability and versatility, but recycling remains a major challenge, especially for mixed or contaminated waste. Mechanical recycling works well for clean, single-polymer streams like PET but has limited efficiency for complex waste streams. Chemical recycling, particularly glycolysis, is often employed to selectively deconstruct condensation polymers under mild conditions. This study explores catalyst design for glycolysis using linear free energy (Hammett) analysis to evaluate how catalyst structure influences polymer deconstruction. Polycaprolactone (PCL) is used as a model polyester due to its solubility and low deconstruction temperature. Triazabicyclodecene (TBD) paired with benzoic acid derivatives depicts a clear linear trend in depolymerization rates with Hammett values. TBD with p-aminobenzoic acid (PABA) stands out for its catalytic efficiency, thermal stability, and scalability, along with PABA's commercial availability as vitamin B-10. The TBD : PABA catalyst not only effectively breaks down PCL but also enables sequential deconstruction of polycarbonate, PET, and Nylon in mixed waste streams. These results highlight the value of Hammett-guided catalyst design and establish TBD : PABA as a promising, scalable organocatalyst for mixed plastic recycling, enabling recovery of individual polymer building blocks from blended waste and offering a practical route toward circular plastics.

Zheng, Jackie [Univ. of Tennessee, Knoxville, TN (↗

Quantitative decoding of the response a ceramic mixed potential sensor array for engine emissions control and diagnostics

The development of on-board sensors for emissions monitoring is necessary for continuous monitoring of the performance of catalytic systems in automobiles. We have fabricated mixed potential electrochemical gas sensing devices with Pt, La 0.8 Sr 0.2 CrO 3 (LSCO), and Au/Pd alloy electrodes and a porous yttria-stabilized zirconia electrolyte. The three-electrode design takes advantage of the preferential selectivity of the Pt + Au/Pd and Pt + LSCO pairs towards different species of gases and has additional tunable selectivity achieved by applying a current bias to the latter pair. Voltages were recorded in single, binary, and ternary gas streams of NO, NO 2 , C 3 H 8 , and CO. We have also trained artificial neural networks to examine the voltage output from sensors in biased and unbiased modes to both identify which single test gas or binary mixture of two test gases is present in a gas stream as well as extract concentration values. We were then able to identify single and binary mixtures of these gases with accuracy of at least 98%. For determining concentration, the peak in the error distribution for binary mixtures was 5% and 80% of test data fell under <12% error. The sensor stability was also evaluated over the course of over 100 days and the ability to retrain ANNs with a small dataset was demonstrated.

33 ADVANCED PROPULSION SYSTEMS↗

Liquid secondary waste: Waste form formulation and qualification

The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, including Direct Feed Low Activity Waste (DFLAW) vitrification, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. The powdered salt waste form produced by the ETF will be replaced by a stabilized solidified waste form for disposal in Hanford’s Integrated Disposal Facility (IDF). Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the IDF. Waste form testing to support this plan is composed of work in the near term to provide data as input to a performance assessment (PA) for Hanford’s IDF. In 2015, three Hanford Liquid Secondary Waste simulants were developed based on existing and projected waste streams. Using these waste simulants, fourteen mixes of Hanford Liquid Secondary Waste were prepared and tested varying the waste simulant, the water-to-dry materials ratio, and the dry materials blend composition.1 In FY16, testing was performed using a simulant of the EMF process condensate blended with the caustic scrubber—from the Low Activity Waste (LAW) melter—, processed through the ETF. The initial EMF-16 simulant will be based on modeling efforts performed to determine the mass balance of the ETF for the DFLAW.2 The compressive strength of all of the mixes exceeded the target of 3.4 MPa (500 psi) to meet the requirements identified as potential IDF Waste Acceptance Criteria in Table 1 of the Secondary Liquid Waste Immobilization Technology Development Plan.3 The hydraulic properties of the waste forms tested (hydraulic conductivity and water characteristic curves) were comparable to the properties measured on the Savannah River Site (SRS) Saltstone waste form. Future testing should include efforts to first; 1) determine the rate and amount of ammonia released during each unit operation of the treatment process to determine if additional ammonia management is required, then; 2) reduce the ammonia content of the ETF concentrated brine prior to solidification, making the waste more amenable to grouting, or 3) manage the release of ammonia during production and ongoing release during storage of the waste form, or 4) develop a lower pH process/waste form thereby precluding ammonia release.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluation of Stream and Wetland Restoration Using UAS-Based Thermal Infrared Mapping

Large-scale wetland restoration often focuses on repairing the hydrologic connections degraded by anthropogenic modifications. Of these hydrologic connections, groundwater discharge is an important target, as these surface water ecosystem control points are important for thermal stability, among other ecosystem services. However, evaluating the effectiveness of the restoration activities on establishing groundwater discharge connection is often difficult over large areas and inaccessible terrain. Unoccupied aircraft systems (UAS) are now routinely used for collecting aerial imagery and creating digital surface models (DSM). Lightweight thermal infrared (TIR) sensors provide another payload option for generation of sub-meter-resolution aerial TIR orthophotos. This technology allows for the rapid and safe survey of groundwater discharge areas. Aerial TIR water-surface data were collected in March 2019 at Tidmarsh Farms, a former commercial cranberry peatland located in coastal Massachusetts, USA (41°54′17″ N 70°34′17″ W), where stream and wetland restoration actions were completed in 2016. Here, we present a 0.4 km2 georeferenced, temperature-calibrated TIR orthophoto of the area. The image represents a mosaic of nearly 900 TIR images captured by UAS in a single morning with a total flight time of 36 min and is supported by a DSM derived from UAS-visible imagery. The survey was conducted in winter to maximize temperature contrast between relatively warm groundwater and colder ambient surface environment; lower-density groundwater rises above cool surface waters and thus can be imaged by a UAS. The resulting TIR orthomosaic shows fine detail of seepage distribution and downstream influence along the several restored channel forms, which was an objective of the ecological restoration design. The restored stream channel has increased connectivity to peatland groundwater discharge, reducing the ecosystem thermal stressors. Such aerial techniques can be used to guide ecological restoration design and assess post-restoration outcomes, especially in settings where ecosystem structure and function is governed by groundwater and surface water interaction.

54 ENVIRONMENTAL SCIENCES↗

Dynamics of Gas Bubbles From a Submarine Hydrocarbon Seep Within the Hydrate Stability Zone

We validate a new model for mass transfer and bubble transport for natural seeps on the continental margins using an integrated observation of a seep at 883 m in the Northern Gulf of Mexico. In the model, mass transfer is assumed to transition from clean to dirty bubble mass transfer rates following a characteristic hydrate formation time that depends on the initial bubble surface area and the hydrate subcooling. We show that buoyancy-induced upwelling is negligible for the bubble stream. We initialize the model using precise data observed at the seafloor and validate the model results to optical and acoustic measurements within the bubble stream. The model accurately predicts the acoustic attenuation of the bubble flare by lateral spreading and bubble shrinkage throughout the water column. In conclusion, the model shows that up to 99.4% by mass of the released gases from this seep dissolves into the ocean within the hydrate stability zone.

03 NATURAL GAS↗

Simultaneous removal of C 2 H 2 and C 2 H 6 for C 2 H 4 purification by robust MOFs featuring a high density of heteroatoms

Simultaneous removal of C 2 H 6 and C 2 H 2 from C 2 H 4 streams is of great importance in the petrochemical industry but remains a challenging task. To address this challenge, we have selected three isoreticular MOFs with high stability, low cost, and desirable scale-up ability, namely, MOF-303, MIL-160, and CAU-23 and assessed their potential in simultaneous removal of acetylene and ethane for ethylene purification. Each MOF exhibits desirable C 2 H 2 and C 2 H 6 uptake capacity (>5.5 mmol g –1 and >4 mmol g –1 , respectively), as well as good C 2 H 2 /C 2 H 4 selectivity (>2) and C 2 H 6 /C 2 H 4 selectivity (>1.5). Notably, MOF-303 takes up 4.96 mmol g –1 C 2 H 6 at 298 K and 1 bar, the highest value among the three MOFs, with C 2 H 6 /C 2 H 4 selectivity in the range of 1.55–2.47. MIL-160 possesses a very high C 2 H 2 uptake (9.1 mmol g –1 ) and C 2 H 2 /C 2 H 4 selectivity, 10.6 (1 : 1, v/v), at 298 K, much higher than those of all other MOFs tested to date for simultaneous removal of C 2 H 6 and C 2 H 2 from C 2 H 4 . The results from breakthrough experiments confirm that all three MOFs demonstrate excellent performance for C 2 H 4 purification in a ternary mixture of C 2 H 6 /C 2 H 4 /C 2 H 2 (1 : 1 : 1, v/v/v). Here, for MOF-303, MIL-160, and CAU-23, polymer-grade C 2 H 4 up to 0.164, 0.21, and 0.181 mmol g –1 can be obtained from the equimolar ternary mixture in a single separation step from the breakthrough experiment. Additionally, DFT calculations have been performed to further investigate the mechanism of adsorption/separation for C 2 H 6 , C 2 H 4 , and C 2 H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonlinear development and secondary instability of Gortler vortices in hypersonic flows

In a hypersonic boundary layer over a wall of variable curvature, the region most susceptible to Goertler vortices is the temperature adjustment layer over which the basic state temperature decreases monotonically to its free stream value. Except for a special wall curvature distribution, the evolution of Goertler vortices trapped in the temperature adjustment layer will in general be strongly affected by the boundary layer growth through the O(M sup 3/2) curvature of the basic state, where M is the free stream Mach number. Only when the local wavenumber becomes as large as of order M sup 3/8, do nonparallel effects become negligible in the determination of stability properties. In the latter case, Goertler vortices will be trapped in a thin layer of O(epsilon sup 1/2) thickness which is embedded in the temperature adjustment layer; here epsilon is the inverse of the local wavenumber. A weakly nonlinear theory is presented in which the initial nonlinear development of Goertler vortices in the neighborhood of the neutral position is studied and two coupled evolution equations are derived. From these, it can be determined whether the vortices are decaying or growing depending on the sign of a constant which is related to wall curvature and the basic state temperature.

Fu, Yibin B.↗

Technetium Stabilization in Low-Solubility Sulfide Phases: A Review

We report that technetium contamination remains a major environmental problem at nuclear reprocessing sites, e.g., the Hanford Site, Washington, USA. At these sites, Tc is present in liquid waste destined for immobilization in a waste form or has been released into the subsurface environment. The high environmental risk associated with Tc is due to its long half-life (214 000 years) and the mobility of the oxidized anionic species Tc(VII)O 4 - . Under reducing conditions, TcO 4 - is readily reduced to Tc(IV), which commonly exists as a relatively insoluble and therefore immobile, hydrous Tc-oxide (TcO 2 · n H 2 O). The stability of Tc(IV) sequestered as solid phases depends on the solubility of the solid and susceptibility to reoxidation to TcO 4 - , which in turn depend on the (biogeo)chemical conditions of the environment and/or nuclear waste streams. Unfortunately, the solubility of crystalline TcO 2 or amorphous TcO 2 ·H 2 O is still above the maximum contaminant level (MCL) established by the U.S. EPA (900 pCi/L), and the kinetics of TcO 2 oxidative dissolution can be on the order of days to years. In addition to oxygen, sulfur can form complexes that significantly affect the adsorption, solubility, and reoxidation potential of Tc, especially Tc(IV). The principal technetium sulfides are TcS 2 and Tc 2 S 7 , but much less is known about the mechanisms of formation, stabilization, and reoxidation of Tc-sulfides. A common assumption is that sulfides are less soluble than their oxyhydrous counterparts. Determination of the molecular structure of Tc 2 S 7 in particular has been hampered by the propensity of this phase to precipitate as an amorphous substance. Recent work indicates that the oxidation state of Tc in Tc 2 S 7 is Tc(IV), in apparent contradiction to its nominal stoichiometry. Technetium is relatively immobile in reduced sediments and soils, but in many cases the exact sink for Tc has not been identified. Experiments and modeling have demonstrated that both abiotic and biologic mechanisms can exert strong controls on Tc mobility and that Tc binding or uptake into sulfide phases can occur. These and similar investigations also show that extended exposure to oxidizing conditions results in transformation of sulfide-stabilized Tc(IV) to a Tc(IV)O 2 -like phase without formation of measurable dissolved TcO 4 - , suggesting a solid-state transformation in which Tc(IV)-associated sulfide is preferentially oxidized before the Tc(IV) cation. This transformation of Tc(IV)-sulfides to Tc(IV)-oxides may be the main process that limits remobilization of Tc as Tc(VII)O 4 - . The efficacy of the final waste form to retain Tc also strongly depends on the ability of oxidizing species to enter the waste and convert Tc(IV) to Tc(VII). Finally, many waste form designs are reducing (e.g., cementitious waste forms such as salt stone) and, therefore, attempt to restrict access of oxidizing species such that diffusion is the rate-limiting step in remobilization of Tc.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Dispersal Limitations on Fish Community Recovery Following Long-term Water Quality Remediation

Holistic restoration approaches, such as water quality remediation, are likely to meet conservation objectives because they are typically implemented at watershed scales, as opposed to individual stream reaches. However, habitat fragmentation may impose constraints on the ecological effectiveness of holistic restoration strategies by limiting colonization following remediation. We questioned the importance of dispersal limitations to fish community recovery following long-term water quality remediation and species reintroductions across the White Oak Creek (WOC) watershed near Oak Ridge, Tennessee (USA). Long-term (26 years) responses in fish species richness and biomass to water quality remediation were evaluated in light of habitat fragmentation and population isolation from instream barriers, which varied in their passage potential. In addition, ordination techniques were used to determine the relative importance of habitat connectivity and water quality, in explaining variation fish communities relative to environmental fluctuations, i.e. streamflow. Ecological recovery (changes in richness) at each site was negatively related to barrier index, a measure of community isolation by barriers relative to stream distance. Following species reintroductions, dispersal by fish species was consistently in the downstream direction and upstream passage above barriers was non-existent. The importance of barrier index in explaining variation in fish communities was stronger during higher flow conditions, but decreased over time an indication of increasing community stability and loss of seasonal migrants. Compared to habitat fragmentation, existing water quality concerns (i.e., outfalls, point source discharges) were unrelated to ecological recovery, but explained relatively high variation in community dynamics. Our results suggest that habitat fragmentation limited the ecological effectiveness of intensive water quality remediation efforts and fish reintroduction efforts by impeding recolonization at isolated stream reaches.

54 ENVIRONMENTAL SCIENCES↗