January 2004

DIAL's Research Highlights

Diagnostic Instrumentation & Analysis Laboratory
Mississippi State University
John Plodinec, Principal Investigator

Prepared for the U.S. Department of Energy
Office of Science and Technology
Cooperative Agreement DE-FC01-04EW54600

Task 1

Support of Closure Sites

Accelerating Phytoremediation by Monitoring Plant Status

During this month, we have been processing the data from the previous phytoremediation experiments and writing papers based on our experimental results. Also during this month, we have received the cold vapor AAS results for the mercury samples we sent to PerkinElmer. The results are consistent with our ICP-AES results, we are in process of preparing the data for publication.

Task 2

Support of Hanford Single Shell Tank Waste Disposition

In-tank/At-tank Characterization for Closure of Hanford Tanks

Stereovision. The current DIAL stereovision system is state-of-the-art. In order to fully document our system, we have been preparation of a paper for publication in a refereed scientific journal.

Microwave-induced plasma-cavity ringdown spectroscopy. The ringdown signal of elemental mercury was observed using our plasma-CRDS system with a compact microwave plasma source. Laser radiation at 254 nm was produced by frequency doubling the output of a Nd:YAG-pumped dye laser. The system's detection sensitivity will be systematically optimized next month. In addition, a blue diode laser source with single mode output around 409 nm was procured. This new laser source will be used as a compact light source for uranium measurements by the plasma-CRDS system.

Fiber optic sensors. A highly sensitive, fast-response photomultiplier tube for scintillation detection has been ordered. This is required to develop an appropriate photodetection system for detection of the scintillation signals. In addition, we are training a GRA student from the MSU Chemistry department to work on sol-gel chemistry.

Fourier transform profilometry. With an emphasis on the internal wires in the FTP Probe, work continued on designing/prototyping a new camera housing and the rotary joint in the robotic FTP-probe for the 4-in. risers on Hanford waste tanks. Modification of the design is dependent upon obtaining a more detailed knowledge of deployment details at Hanford. The search for sources for bright utility and projector lights continued as did work on the control cable manufacture and the software development for the new camera control and image acquisition software. Our efforts on image quality improvement continued.

Information sifting. The information sifting effort has completed implementation of capability of uploading spectra for addition of spectra to the library. In addition, a deletion tool has been added, permitting a user to select a library and delete any of the spectra in the selected library.

Process Chemistry and Operations Planning for Hanford Waste Alternatives

ESP model calculations have been started on the dissolution of salt cake waste in HNF tank S-102.

Projected aqueous streams from these simulations are being evaluated with an evaporation model to assess the waste volume reduction factor and to understand the crystallization of specific solids as the evaporator streams are cooled. Earlier calculations with the salt waste from tank S-112 indicated that sulfate solids can be separated from NaNO₃ indicating that some pretreatment of the evaporator streams was possible prior to routing the waste to the glass plant.

Aluminum solubility studies are continuing. Experiments containing higher initial molalities of aluminum with NaNO₃ have been prepared and analytical results are in process. The experimental system NaAlO₂/Na₂CO₃/H₂O at 25°C has been prepared and is approaching equilibrium. Past studies of some aluminum systems have shown long equilibrium times (up to 6 months) even when precipitation has occurred. Experiments are currently being designed to determine when aluminum equilibrium has been attained in each of the systems. Regression calculations are underway for the data collected for the Na₂SO₄/Na₃PO₄ systems and will be included in the DBLSLTDB database.

Flexible Scintillating Optical Fiber Sensor for Determination of Liquid Level

Light guiding efficiency tests have been performed for the light guiding flexible fused silica capillary (Polymicro Technologies, LLC) that is the core of the scintillating optical fiber sensor. Although satisfactory signals were obtained by coupling conventional light sources to the capillary, improved light guiding capabilities are desired. Therefore, light guiding capillary of 50 and 150 mm inner diameter was purchased in an effort to increase the modal capacity of the silica tubing. In addition, a light guiding capillary bundle was tested with encouraging preliminary results.

The HAMAMATSU HC135-11 has been ordered. This detection system is packaged with a micro-controller and RS-232-C interface. Production will take six weeks, at which time the system will be set-up in the laboratory for preliminary experimentation.

Laboratory tests will focus on improving the light guiding efficiency of the light guiding flexible fused silica capillary. In addition, optimization of the coating procedure will continue.

Tank Leak Detection and Monitoring System

Vigorous efforts were focused on the procurement of the major components of the tank leak detection system (TLDS). A special ringdown gas cell adopted from a commercial ringdown product was modified to be used in the TLDS. This gas cell was ordered. Other major components such as the laser source, ringdown mirrors, and associated mechanical parts of the TLDS were ordered. We were also working on the design of the blueprint of the TLDS. Once all the parts are delivered, the assembly and alignment of the system for the laboratory-level testing will start. The progress of the project is on schedule.

Task 3

Disposition of Idaho HLW Calcine

Support of INEEL Calcine Disposition Project

January 2003 was the 4th project month. In January, DIAL researchers received the formal guidance on calcine stabilizers. The waste forms selected include an iron-phosphate ceramic, grout, tin-zinc-phosphate glass, and hydro ceramics. Towards the end of the month, two samples of simulated calcine were received.

Specific activities were undertaken towards work scope item 3 for FY 2004:

Simulant composition verification. DIAL analytical laboratories will provide a chemical composition of the calcine simulant to the INEEL Stabilization Lead. This will be provided for an INEEL review of DIAL laboratory capabilities.

The simulant samples have been split and submitted for weight loss (on drying), chemical analysis, TCLP, and PCT. These data will provide a check of the DIAL analytical laboratory as well as baseline performance data.

Specific activities were undertaken towards work scope item 4 for FY 2004:

Waste form production. Waste forms will be generated at the DIAL lab using INEEL approved simulant.

Chemical supplies have been ordered for waste form production. A review of waste form versus existing equipment was made; no additional production equipment was deemed essential. A mercury analyzer is being procured for the analytical lab. This equipment is being shared with another cooperative agreement project (use and procurement cost).

Weekly reports of analytical and performance testing will be provided to Tom Thomas (project oversight) of INEEL beginning 2/6/04.

Task 4

Support of SRS Salt Disposition and Other SRS Alternatives

Support for SRS Salt Disposition Alternatives

An extensive literature search was performed for data on aluminum and silicon thermodynamics and solubilities. Data collected from the literature is in the process of being assembled in tabular form for inclusion in development of the sodium aluminum silicates (NAS) database.

ESP modeling of Tank 38H and 37H is currently being investigated for stimulant preparation for flow through and DASR experiments. Property relationships from tank 41H experiments at differing temperatures were examined and transferred to SRS.

On-line Analysis for Defense Waste Processing Facility

LIBS data from the pellet of the RIC glass batch were collected with Echelle spectrometer. All the major and minor species were identified from the observed spectra. The linear calibration curves for major species were obtained. The precision of these data is better than 5%. To evaluate the possibility to direct analyze the power sample (RIC_Blind_200 and EA glass power), we have kept the power samples on a double-sided adhesive tape mounted on a microscope slide. The precision of these data has poor precision (10 - 15%). The poorer precision is due to the inhomogeneous distribution of the power on the sample mount. However, a normalization procedure can be applied to the data to improve the precision. To obtain the calibration data for the EA glass, we will prepare the glass batch with different Li and Fe ratio. The required chemicals to simulate the DWPF glass, which are not available in DIAL have been ordered. Drs. Singh and Ramsey will visit SRS in February to discuss the various issues related with the DWPF project.

Support of Production of High Waste Loading Glasses in the DWPF

January 2004 was the fourth project month. DIAL researchers reviewed three documents provided by Dr. David Peeler of WSRC:

• WSRC-TR-2001-00148
• WSRC-TR-2001-00131
• WSRC-TR-2001-00351

These documents detail melt rate, cold cap modeling, and glass formulation studies performed at the SRS in support of Hanford and Savannah River waste vitrification programs. Using this material as a guide, DIAL is developing a test plan for Subtask 1 for WSRC review.

Subtask 1. Melt chemistry experiments. DIAL will carry out a series of experiments to better understand the chemistry of the cold cap, specific to glasses with higher waste loading. These experiments will utilize both "after-the-fact" techniques (e.g., SEM) as well as real-time instrumentation to determine the chemistry of the reactions that are occurring during melting of high level waste glasses, both in the melting feed and in the gas phase.

DIAL is planning to acquire simulated sludge, melter feed slurry and glass frit. Small (150 ml) scale crucible melts will be performed and the resulting heat-treated materials analyzed using standard SEM and proprietary DIAL methods. The task goal is to provide a metric and method for predicting melt rate from melter feed chemistry.

An equipment review was made. No large-scale equipment is deemed essential. Procurements of crucibles and insulating refractory have been made. Fabrication of new head-pieces for existing furnace have begun. These heads will allow optical access for in situ melt rate studies.

Samples of an SRS glass standard and palletized batch material are being prepared for laser induced breakdown spectroscopy (LIBS). This effort (led by Dr. J. P. Singh) will determine the applicability of LIBS as a tool for DWPF melter feed and in situ pour stream composition analysis.

Task 5

HEPA Filter Performance Assurance

Regenerable HEPA Filter Performance Testing

During the month of January, preliminary work was done on the steam testing. The air entering the test stand was heated using two large capacity heaters capable of supplying 90 kW power. A water spray was added to increase the relative humidity in the test stand. The test was conducted at 150°F and 200°F. The relative humidity reached 65% in the test stand. DIAL is looking at some better methods for producing steam in the test stand, possibly an industrial steam generator.

Preparation of papers for presentation at the March 2004 Waste Management Conference began.

In the calibration laboratory, calibration of all instrumentation (ELPI, SMPS, and CPC) was performed. More work was conducted in comparing ELPI and EPA Reference Method 5i.

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