Recalibration of H Canyon Online Spectrophotometer at Extended Uranium Concentration

The H Canyon online spectrophotometers are calibrated for measurement of the uranium and nitric acid concentrations of several tanks in the 2nd Uranium Cycle.[1] The spectrometers, flow cells, and prediction models are currently optimized for a process in which uranium concentrations are expected to range from 0-15 g/L and nitric acid concentrations from 0.05-6 M. However, an upcoming processing campaign will involve 'Super Kukla' material, which has a lower than usual enrichment of fissionable uranium. Total uranium concentrations will be higher, spanning approximately 0-30 g/L U, with no change in the nitric acid concentrations. The new processing conditions require the installation of new flow cells with shorter path lengths. As the process solutions have a higher uranium concentration, the shorter path length is required to decrease the absorptivity to values closer to the optimal range for the instrument. Also, new uranium and nitric acid prediction models are required to span the extended uranium concentration range. The models will be developed for the 17.5 and 15.4 tanks, for which nitric acid concentrations will not exceed 1 M. The restricted acid range compared to the original models is anticipated to reduce the measurement uncertainty for both uranium and nitric acid. The online spectrophotometers in H Canyon Second Uranium Cycle were modified to allow measurement of uranium and nitric acid for the Super Kukla processing campaign. The expected uranium concentrations, which are higher than those that have been recently processed, required new flow cells with one-third the optical path length of the existing cells. Also, new uranium and nitric acid calibrations were made. The estimated reading uncertainties (2{sigma}) for Tanks 15.4 and 17.5 are {approx}5% for uranium and {approx}25% for nitric acid

Evaluation of Miniaturized Infrared Sensors for Process Control of the Palladium Membrane Reactor

We have tested the suitability of a miniaturized infrared sensor for measurements of CO and H{sub 2}O in the inlet stream to the Palladium Membrane Reactor (PMR). We demonstrated that both analytes can be measured with absolute accuracies of 2-4% at the process inlet conditions of 120-140 C and approximately 1 atm of each gas. This accuracy must be improved to 1-1.5% for effective PMR process control. The use of a reference detector and independent temperature and pressure measurements to correct the raw signals will improve the accuracy to a level that will approach, if not meet, this goal. With appropriate bandpass filters, the infrared sensors may be used for other gas analysis applications

THE AFFECTS OF HALIDE MODIFIERS ON THE SORPTION KINETICS OF THE LI-MG-N-H SYSTEM

In this present work, the affects of different transition metal halides (TiCl{sub 3}, VCl{sub 3}, ScCl{sub 3} and NiCl{sub 2}) on the sorption properties of the 1:1 molar ratio of LiNH{sub 2} to MgH{sub 2} are investigated. The modified mixtures were found to contain LiNH{sub 2}, MgH{sub 2} and LiCl. TGA results showed that the hydrogen desorption temperature was reduced with the modifier addition in this order: TiCl{sub 3}>ScCl{sub 3}>VCl{sub 3}>NiCl{sub 2}. Ammonia release was not significantly reduced resulting in a weight loss greater than the theoretical hydrogen storage capacity of the material. The isothermal sorption kinetics of the modified systems showed little improvement after the first dehydrogenation cycle over the unmodified system but showed drastic improvement in rehydrogenation cycles. XRD and Raman spectroscopy identified the cycled material to be composed of LiH, MgH{sub 2}, Mg(NH{sub 2}){sub 2} and Mg{sub 3}N{sub 2}

Evaluation of Technologies to Complement/Replace Mass Spectrometers in the Tritium Facilities

The primary goal of this work is to determine the suitability of the Infraran sensor for use in the Palladium Membrane Reactor. This application presents a challenge for the sensor, since the process temperature exceeds its designed operating range. We have demonstrated that large baseline offsets, comparable to the sensor response to the analyte, are obtained if cool air is blown across the sensor. We have also shown that there is a strong environmental component to the noise. However, the current arrangement does not utilize a reference detector. The strong correlation between the CO and H{sub 2}O sensor responses to environmental changes indicate that a reference detector can greatly reduce the environmental sensitivity. In fact, incorporation of a reference detector is essential for the sensor to work in this application. We have also shown that the two sensor responses are adequately independent. Still, there are several small corrections which must to be made to the sensor response to accommodate chemical and physical effects. Interactions between the two analytes will alter the relationship between number density and pressure. Temperature and pressure broadening will alter the relationship between absorbance and number density. The individual effects are small--on the order of a few percent or less--but cumulatively significant. Still, corrections may be made if temperature and total pressure are independently measured and incorporated into a post-analysis routine. Such corrections are easily programmed and automated and do not represent a significant burden for installation. The measurements and simulations described above indicate that with appropriate corrections, the Infraran sensor can approach the 1-1.5% measurement accuracy required for effective PMR process control. It is also worth noting that the Infraran may be suitable for other gas sensing applications, especially those that do not need to be made in a high-temperature environment. Any gas with an infrared absorption (methane, ammonia, etc.) may be detected so long as an appropriate bandpass filter can be manufactured. Note that homonuclear diatomic molecules (hydrogen and its isotopes, nitrogen, oxygen) do not have infrared absorptions. We have shown that the sensor response may be adequately predicted using commercially available software. Measurement of trace concentrations is limited by the broad spectral bandpass, since the total signal includes non-absorbed frequencies. However, cells with longer pathlengths can be designed to address this problem

Botulinum Neurotoxin Devoid of Receptor Binding Domain Translocates Active Protease

Clostridium botulinum neurotoxin (BoNT) causes flaccid paralysis by disabling synaptic exocytosis. Intoxication requires the tri-modular protein to undergo conformational changes in response to pH and redox gradients across endosomes, leading to the formation of a protein-conducting channel. The ∼50 kDa light chain (LC) protease is translocated into the cytosol by the ∼100 kDa heavy chain (HC), which consists of two modules: the N-terminal translocation domain (TD) and the C-terminal Receptor Binding Domain (RBD). Here we exploited the BoNT modular design to identify the minimal requirements for channel activity and LC translocation in neurons. Using the combined detection of substrate proteolysis and single-channel currents, we showed that a di-modular protein consisting only of LC and TD was sufficient to translocate active protease into the cytosol of target cells. The RBD is dispensable for cell entry, channel activity, or LC translocation; however, it determined a pH threshold for channel formation. These findings indicate that, in addition to its individual functions, each module acts as a chaperone for the others, working in concert to achieve productive intoxication

Application of Absorption Spectroscopy to Actinide Process Analysis and Monitoring

The characteristic strong colors of aqueous actinide solutions form the basis of analytical techniques for actinides based on absorption spectroscopy. Colorimetric measurements of samples from processing activities have been used for at least half a century. This seemingly mature technology has been recently revitalized by developments in chemometric data analysis. Where reliable measurements could formerly only be obtained under well-defined conditions, modern methods are robust with respect to variations in acidity, concentration of complexants and spectral interferents, and temperature. This paper describes two examples of the use of process absorption spectroscopy for Pu analysis at the Savannah River Site, in Aiken, SC. In one example, custom optical filters allow accurate colorimetric measurements of Pu in a stream with rapid nitric acid variation. The second example demonstrates simultaneous measurement of Pu and U by chemometric treatment of absorption spectra. The paper concludes with a description of the use of these analyzers to supplement existing technologies in nuclear materials monitoring in processing, reprocessing, and storage facilities

EFFECTS OF TRITIUM GAS EXPOSURE ON ELECTRICALLY CONDUCTING POLYMERS

Effects of beta (tritium) and gamma irradiation on the surface electrical conductivity of two types of conducting polymer films are documented to determine their potential use as a sensing and surveillance device for the tritium facility. It was shown that surface conductivity was significantly reduced by irradiation with both gamma and tritium gas. In order to compare the results from the two radiation sources, an approximate dose equivalence was calculated. The materials were also sensitive to small radiation doses (<10{sup 5} rad), showing that there is a measurable response to relatively small total doses of tritium gas. Spectroscopy was also used to confirm the mechanism by which this sensing device would operate in order to calibrate this sensor for potential use. It was determined that one material (polyaniline) was very sensitive to oxidation while the other material (PEDOT-PSS) was not. However, polyaniline provided the best response as a sensing material, and it is suggested that an oxygen-impermeable, radiation-transparent coating be applied to this material for future device prototype fabrication. A great deal of interest has developed in recent years in the area of conducting polymers due to the high levels of conductivity that can be achieved, some comparable to that of metals [Gerard 2002]. Additionally, the desirable physical and chemical properties of a polymer are retained and can be exploited for various applications, including light emitting diodes (LED), anti-static packaging, electronic coatings, and sensors. The electron transfer mechanism is generally accepted as one of electron 'hopping' through delocalized electrons in the conjugated backbone, although other mechanisms have been proposed based on the type of polymer and dopant [Inzelt 2000, Gerard 2002]. The conducting polymer polyaniline (PANi) is of particular interest because there are extensive studies on the modulation of the conductivity by changing either the oxidation state of the main backbone chain, or by protonation of the imine groups [de Acevedo, 1999]. There are several types of radiation sensors commercially available, including ionization chambers, geiger counters, proportional counters, scintillators and solid state detectors. Each type has advantages, although many of these sensors require expensive electronics for signal amplification, are large and bulky, have limited battery life or require expensive materials for fabrication. A radiation sensor constructed of a polymeric material could be flexible, light, and the geometry designed to suit the application. Very simple and inexpensive electronics would be necessary to measure the change in conductivity with exposure to radiation and provide an alarm system when a set change of conductivity occurs in the sensor that corresponds to a predetermined radiation dose having been absorbed by the polymer. The advantages of using a polymeric sensor of this type rather than those currently in use are the flexibility of sensor geometry and relatively low cost. It is anticipated that these sensors can be made small enough for glovebox applications or have the ability to monitor the air tritium levels in places where a traditional monitor cannot be placed. There have been a few studies on the changes in conductivity of polyaniline specifically for radiation detection [de Acevedo, 1999; Lima Pacheco, 2003], but there have been no reports on the effects of tritium (beta radiation) on conducting polymers, such as polyaniline or polythiophene. The direct implementation of conducting polymers as radiation sensor materials has not yet been commercialized due to differing responses with total dose, dose rate, etc. Some have reported a large increase in the surface conductivity with radiation dose while others report a marked decrease in conductive properties; these differing observations may reflect the competing mechanisms of chain scission and cross-linking. However, it is clear that the radiation dose effects on conducting polymers must be fully understood before these materials can be used as sensing devices. This report presents the results of irradiations of two conductive polymers: polyaniline and polythiophene. Samples of doped polyaniline and polythiophene were coated onto polyester (polyethyleneterephalate, PET) substrates and were exposed to both tritium gas (beta irradiation) and {sup 60}Co gamma irradiation. The samples were subsequently characterized after various total doses. Infrared spectroscopy was utilized to characterize the gamma-exposed samples post-irradiation. Although the sources of radiation are different in kind (charged particle versus photon) and their energies differ, there will be great value in using noncontaminating gamma irradiation to model the effects of tritium beta radiation

THE EFFECTS OF HALIDE MODIFIERS ON THE SORPTION KINETICS OF THE LI-MG-N-H SYSTEM

The effects of different transition metal halides (TiCl{sub 3}, VCl{sub 3}, ScCl{sub 3} and NiCl{sub 2}) on the sorption properties of the 1:1 molar ratio of LiNH{sub 2} to MgH{sub 2} are investigated. The modified mixtures were found to contain LiNH{sub 2}, MgH{sub 2} and LiCl. TGA results showed that the hydrogen desorption temperature was reduced with the modifier addition in this order: TiCl{sub 3} > ScCl{sub 3} > VCl{sub 3} > NiCL{sub 2}. Ammonia release was not significantly reduced resulting in a weight loss greater than the theoretical hydrogen storage capacity of the material. The isothermal sorption kinetics of the modified systems showed little improvement after the first dehydrogenation cycle over the unmodified system but showed drastic improvement in rehydrogenation cycles. X-ray diffraction and Raman spectroscopy identified the cycled material to be composed of LiH, MgH{sub 2}, Mg(NH{sub 2}){sub 2} and Mg{sub 3}N{sub 2}

Opportunities and Challenges of Offsite Construction

The interest in offsite construction technology continues to grow as project stakeholders are becoming increasingly comfortable with this modern and transformational construction method and its outcomes. While different studies have been conducted to investigate multiple aspects of offsite construction, there is still a lack of research that was directed to study the opportunities and challenges of offsite construction for the workforce. As such, this study addresses this knowledge gap by examining the workforce implications of offsite construction. To this end, the authors followed a methodology consisting of the interrelated review of previous studies as well as the analysis of industry experts\u27 opinions. First, literature review was performed to identify different workforce properties. Second, a survey was designed and distributed to industry experts to understand their perceptions on the identified workforce properties. Third, the implications of offsite construction were quantified using descriptive statistics based on the obtained responses. The findings reflected that offsite construction could create: (1) many opportunities for the workforce including greater productivity, higher learning rate, better working conditions, enhanced worker quality, and improved safety and health, among others, and (2) some challenges for the workforce including longer career path progression, higher cost of training and development, and displacement of local workers, among others. Ultimately, this study adds to the body of knowledge by helping practitioners in better understanding and quantifying the key workforce opportunities and challenges of offsite construction