January 2007

Monthly Research Progress


Institute for Clean Energy Technology
(formerly Diagnostic Instrumentation & Analysis Laboratory)
Mississippi State University
Roger King, Interim Director


Prepared for the U.S. Department of Energy
Office of Science and Technology
Cooperative Agreement DE-FC01-06EW07040


Task 1

Support of Oak Ridge Site Closure

Characterization of Corrosion for Closure of Oak Ridge Research Reactor

Because of lack of funds for the end of the 2006 federal fiscal year, our Oak Ridge collaborators were unable to provide the support required to enable deployment into the Oak Ridge Research Reactor (ORRR) pool during September.

Task 2

Support of Hanford Single Shell Tank Waste Disposition

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

Stereovision. Progress on the stereovision effort was significantly slowed during January by the unexpected departure in December of the graduate student working on this effort.

Fourier transform profilometry. During January, the Fourier transform profilometry (FTP) effort continued to validate performance by use of synthetic images generated analytically. These synthetic images which simulate target surfaces at a distance of 20 feet from camera were subsequently processed with the FTP analysis software. This analysis of synthetic images where the target object is fully contained with a single image resulted in errors of less than 1% of the actual volume of the target surface. The target object was a right circular cone with radius and height of 15 cm and thus a volume of 3534 cm3. This initial use of our FTP simulator mimics measurement conditions where the tank floor is directly under the tank riser used for camera access. In this area of the tank, the tank surface is mostly perpendicular to the camera optical axis and has insignificant curvature.

Through the use of the simulator we were also able to identify a problem with code used for stitching volume contributions of target object portions contained in separate but overlapping images. The effort spent on developing this capability to simulate the FTP instrument should prove its anticipated usefulness for verifying FTP data quality in the future.

Some effort was also spent to measure the shape of the full-scale "prop" surface which was constructed to allow target objects to be measured on surface such as will be encountered in the "heel" area of the S-100 series tanks. The prop surface has very good precision in the tangential direction, but lack of incorporated reference data made determination of accuracy of the surface in the radial direction more difficult than originally anticipated.

Process Chemistry and Operations Planning for Hanford Waste Alternatives

Calculations were finished for the aluminum solubility experiments conducted in starting caustic loadings of 1, 3 and 7 m. Results from the experiments were in excellent agreement with ESP (Version 7.) and Stream Analyzer (Version 2.0). This indicated that efforts by OLI personnel in upgrading the Public database for aluminum in caustic solution have been largely successful.

Work on converting gibbsite to boehmite continues with solution studies at 125°C. Here, after a period of only three hours, the starting material was converted to about 90% AlOOH. Additional experiments are being conducted at lower temperatures to assess the conditions under which the difficult to dissolve boehmite may form. Some discrepancies were observed in companion ESP calculations where the primary solid predicted at 80°C was gibbsite, but where the scaling tendency for boehmite was greater than one indicating that the solid should also form.

Work on neural network development has concerned identifying a means where ESP calculations and analysis can be automated. Script language software is being evaluated so that calculations can be done automatically. It is expected, but not yet known, that the compositional range of the developed neural networks can be extended so as to provide for improved predictive capability.

Discussions with OLI Systems Inc. on porting the V7DBLSLT database to the mixed solvent electrolyte (MSE) formalism are continuing. Initial quotes for the project have exceeded the subcontract value of the work planned here for 2007; consequently the process of prioritizing the systems to be included in the database has begun.


Task 3

Disposition of Idaho HLW Calcine

Support of CH2M-WG Calcine Disposition Project

The feeders, mixers and control equipment are now being installed on the test stand for the mock-up system. We expect to begin shakedown testing of the mock-up in the next week or two (depending on the weather).

We made two sets of cubes (17% and 34%) in December to test for mechanical strength. No anomalies were observed during mixing, however, neither set appears to be curing as before. We aged them for a total of 37 days and then tested them in compression. The results below show that both formulations are sufficiently strong after that period of time.

We also made up a larger batch with this simulant (with the hopes that scaling up will give better results). After seven days, only the 34% cubes had cured; the compression tests are given below. They are not quite strong enough at this point. We have saved three other cubes to be tested after 28 days with the 17% formulation.

Sample Maximum
Load (lbs)
Stress (psi)
Time (days)
12G34A 5302 1326 37
12G34B 4843 1211 37
G17A 2954 739 37
G17B 3648 912 37
G17C 3413 853 37
G34A 1704 426 7
G34C 1858 465 7


Task 4

Support of SRS Salt Disposition and Other SRS Alternatives

Modeling and Experimental Support for High-level SRS Waste Disposition

The KNO3/NaNO3 systems prepared in water, 1-m and 3-m NaOH solutions at 25°C have undergone analysis and have been readied for regressions. The CsNO3/NaNO3 systems in water, 1-m and 3-m caustic at 25°C have reached equilibrium and the solutions are being prepared for analysis.

Results from the solubility studies of the Al/NaNO3/NaOH systems, examples of solids formation occurring during salt cake dissolution experiments, and preliminary results from the gibbsite/boehmite transition experiments currently being investigated were presented at the SRS Al/Cr leaching workshop held in Atlanta this month.

Process Improvements for the Defense Waste Processing Facility (DWPF): On-line Analysis

Work on the new subtask of analyzing the plutonium oxide residues began. A fiber optic LIBS system is being designed to deliver the laser pulse to the sample surface. The sample will be kept inside the glove box while the LIBS system will be outside of the glove box. To design a fiber optics system for long-term operation, we will need to determine the ranges of laser energy that can be delivered by optical fiber to produce breakdown in sample surface without damaging the fiber. Different optical designs for coupling the laser beam with optical fiber will be tested. The various lenses that are needed to expand the laser beam and focus the laser beam are being ordered. To reduce the cost in the initial parametric study, the homemade optical fibers will be used in the initial test. Due to the practical consideration, the sample in the test facility will be in pellet form and retained in its press container. To test our LIBS system with the sample similar to the one in the test facility, a pellet container that can be used to press the sample was designed and fabricated. The different chemicals to prepare the pellet of the surrogate of the plutonium oxide power were ordered.

Process Improvements for the Defense Waste Processing Facility (DWPF): Improvement of Waste Throughput

X-ray Diffraction (XRD) experiments on SB4 simulant with Frits 418 and 503 were begun this quarter. Materials heated to 600°C, 700°C and 800°C are being examined. It is clear that there are new phases appearing as other phases disappear with increased temperature. The most interesting appearing/disappearing phases are two major phases of silica, cristobalite and tridymite. There may also be lithium silicate and lithium disilicate. The changes of these phases in these melts could provide insight to the over all melting behavior.

Process Improvements for the Defense Waste Processing Facility (DWPF): Melter Monitoring

Discussions have been started on a task involving using ICET diagnostic instrumentation to assist with melting studies using the Cold Cap Evaluation Furnace (CEF) which has been built at SRNL. A conference call was held to discuss the pros and cons of various methods of monitoring, concentrating on the problem of minimizing the fouling of windows by gases generated within the furnace. This task will be a large part of our effort in the coming year.


Task 5

DOE Headquarters Support

DOE HQ Road Map

ICET participated in the Road Map development activities by EM-20 during the latter part of the 2006 calendar year. ICET’s Interim Director and Deputy Director attended two general meetings at DOE Headquarters in which road mapping was discussed. Additionally, the Deputy Director took part in the Road Mapping Workshop held at Headquarters during November.

Workshop on Heavy Metal Phytoremediation

ICET will host a workshop on the application of remote sensing to environmental monitoring. The workshop will be held in Starkville, Mississippi during the second or third quarter of 2007. Workshop planning will be a coordinated effort between personnel representing EM-20 at DOE Headquarters, Savannah River National Lab, and ICET. The workshop will focus on developing a two year research plan for developing and evaluating tools enabling use of remote sensing as a monitoring tool. Targeted monitoring parameters will include: contaminant plume migration, status of vegetation used in bioremediation, and ecological recovery from releases.

HEPA and Regenerable Filter Performance Assurance

A filter housing designed to facilitate load/air back pulse testing of large Ceramem regenerable filters was assembled. The test bed also assembled. Minor modifications were made to the HEPA filter test stand to setup the regenerable filter test bed. Preliminary testing was done to make sure that the SMPS could sample against the line pressure as well as achieving proper air flow rate in the test bed. It was determined that the SMPS would sample under the test conditions. Work to be completed includes integrating pressure transducers and possibly a control valve into the existing computer system on the larger HEPA filter test stand.

Bio-availability Studies of Mercury and Other Heavy Metal Contaminants in Ecosystems of Selected DOE Sites

This month we started a series of new experiments on stability and bioavailability of HgS-contaminated Oak Ridge soils. The goal of these experiments is to unveil the mechanisms governing biogeochemical processes for the most recent increase in concentrations of both total mercury and methylmercury in fish and water of lower East Fork Poplar Creek (LEFPC) of Oak Ridge, although the majority of mercury in the site is in mercury sulfide form. The experiments include the reaction kinetics of soil HgS with iron/manganese oxides which are widely present in soils and sediments. The release kinetics of mercury from soil HgS by complexing agents such as EDTA and oxalate acids, which are present in rhizophere soils were also studied.

In February, we will continue these experiments and may initiate the new experiments on reaction kinetics of soil HgS with elemental S and sulfide, which are possibly triggering the increase of Hg concentrations in Oak Ridge site.

Phytoremediation and Long-term Monitoring of Selected Heavy Metal and Radionuclide Contaminants

During this month, we have been analyzing samples and data from previous experiments. We are preparing soils and plants for new experiments, which will start in the coming months.

Task 6

Technology Development

Development of New Technologies for DOE Site Applications

Currently, two new technologies, plasma-CRDS for trace radionuclides monitoring and waveguide ringdown optical modules for tank vapor detections, are being developed. In this month, a new optical module operating in the near-IR spectral region was tested with atmospheric molecules, such as CO2 and CH4. The purpose of the test is to evaluate the ruggedness of the module in simulated vibration environments. Multiplexing dual diode laser sources in two different spectral regions for detection of multiple species will be investigated next month.

Development of Fiber Optic Sensor Technologies for DOE Site Applications

The work of the fiber optic sensor group this month was focused on building up our liquid core waveguide fiber optic system. The purpose of this work is to build up a highly sensitive spectroscopic system for observation of radiolysis-induced chemical reactions. The radiolysis-induced chemical reactions in the waste tanks affect the chemical forms of organic and inorganic compounds in the waste. Therefore, the comprehension of radiolysis-induced chemical reactions could provide information regarding the chemical forms of organic and inorganic compounds in the waste tanks.


Inquiries may be addressed to:

Dr. Roger King, Interim Director
205 Research Blvd.
Starkville, MS 39762-5932


Phone: 662-325-2105
FAX: 662-325-8465
Email: icet@icet.msstate.edu