Laser Induced Breakdown Spectros

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Laser-induced breakdown spectroscopy (LIBS)
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Technology Demonstration
and Verification Research
Quarterly Technical Progress Report

for the period
April 1, 1998 - September 30, 1998
Dr. John Plodinec, Principal Investigator
October 1998
Prepared for the U.S. Department of Energy

Agreement No. DE-FT26-98FT40395
Diagnostic Instrumentation and Analysis Laboratory

Mississippi State University
205 Research Boulevard
Starkville, Mississippi 39759-9734
dial@dial.msstate.edu
www.msstate.edu/Dept/DIAL
Notice
This report was prepared as an account of work sponsored by an agency of the
United States Government. Neither the United States Government nor any agency
thereof, nor any of their employees, makes any warranty, express or implied, or
assumes any legal liability or responsibility for the accuracy, completeness, or use-
fulness of any information, apparatus, product or process disclosed or represents
that its use would not infringe privately-owned rights. Reference herein to any spe-
cific commercial product, process, or service by trade name, trademark, manufac-
turer, or otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or nay agency
thereof. The views and opinions of authors expressed therein do not necessarily
state or reflect those of the United States Government or any agency thereof.
Table of Contents
Abstract ................................1
TASK 1 Verification Monitors for Thermal

Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Subtask 1.1. Monitors for Thermal Processes . . . . . . . . . . . 3
Air Plasma Off-gas Emission Monitor (APO-GEM) . . . . . 4
Laser-induced Breakdown Spectroscopy . . . . . . . . . . . . . 14
Subtask 1.2. Mercury Absorber Technology . . . . . . . . . . . 18
TASK 2 Deactivation and Decommissioning

Technology Support . . . . . . . . . . . . . . . . . . . . . 20
Subtask 2.1. Pipecleaning Technology . . . . . . . . . . . . . . . . 20
Subtask 2.2. Wall Removal Monitor . . . . . . . . . . . . . . . . . . 23
DIAL 40395-1 iii

Contents
TASK 3 Technical Data to Support Cleanup

Decisions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Subtask 3.1. Dioxins/Furans in Incinerator Burner . . . . . . 26
Dioxin Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Detection of Chlorinated Organics
by Cavity Ring-down Spectroscopy . . . . . . . . . . . . . . . . 29
Subtask 3.2. Dissolution of Hanford Salt . . . . . . . . . . . . . . 32
TASK 4 Product Acceptance Support . . . . . . . . . . . . . . 56

Subtask 4.1. Monitors for Idaho LAW Stream . . . . . . . . . . 56
Subtask 4.2. Pressure in Drums . . . . . . . . . . . . . . . . . . . . . 67
TASK 5 Advanced Cleanup Support:

Robust Immobilization Devices . . . . . . . . . . . . 71
Subtask 5.1. Hybrid Plasma Induction Cold Crucible
Melter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Subtask 5.2. Hollow-electrode DC Arc Furnace for
Mixed-waste Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . 78
DIAL 40395-1 iv
List of Figures
FIGURE 1. Schematic of APO-GEM continuous emission

monitor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
FIGURE 2. The effect of moisture on the emission of Mg in an
air-plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
FIGURE 3. ICP emission spectra obtained using the AOTF-echelle
spectrometer, illustrating the resolution of the system . . 12
FIGURE 4. LIBS signal (a) and background (b) as a function
of laser energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
FIGURE 5. S/B as a function of laser energy . . . . . . . . . . . . . . . . . . 17
FIGURE 6. Results for 1,4-dichlorobenzene . . . . . . . . . . . . . . . . . . . 31
FIGURE 7. Block diagram of the solubility apparatus. . . . . . . . . . 38
FIGURE 8. KCl solubilities determined with the experimental
apparatus and compared to literature data and ESP
model results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
FIGURE 9. Solubilities of Na3PO4 . . . . . . . . . . . . . . . . . . . . . . . . 39
FIGURE 10. Predicted solubility envelope for Na7F(PO4)2.19H2O . . 41
DIAL 40395-1 v
Figures
FIGURE 11. Comparison of experimental and predicted results

for nitrate anion concentration – Tank BY-106. . . . . . . . 44
FIGURE 12. Comparison of experimental and simulation
results for sulfate anion – Tank BY-106 (25°C) . . . . . . . 45
FIGURE 13. Predicted solids mass in SY-101 during in situ
dilution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
FIGURE 14. Schematic of cavity-ringdown spectroscopy technique . 58
FIGURE 15. Schematic of the laser-induced fluorescence
spectrometry technique . . . . . . . . . . . . . . . . . . . . . . . . . . 59
FIGURE 16. Schematic of isotopic energy shifts and the associated
LIF spectrum. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
FIGURE 17. Cavity ringdown decay for air with mirrors optimized
for 360-nm operation . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
FIGURE 18. Cavity ringdown spectrum of atomic chromium
absorption at 357.9 nm . . . . . . . . . . . . . . . . . . . . . . . . . . 62
FIGURE 19. Schematic of hybrid plasma induction cold crucible
melter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
FIGURE 20. DC arc furnace at Montec Associates, Butte, MT . . . . . 79
FIGURE 21. DC arc furnace at Montec Associates, Butte,
MT, July 1998 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
FIGURE 22. Feeder for the hollow-electrode DC arc heater
experiment, Montec Associates, Butte, MT, July
1998. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
FIGURE 23. Hollow-electrode dc arc heater at Montec Associates,
Butte, MT, July 1998 . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
FIGURE 24. Off-gas species concentration during bulk-solid
addition, Montec Associates, Butte, MT, August
1998. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
FIGURE 25. Dissolution of the refractory bricks . . . . . . . . . . . . . . . . 86
DIAL 40395-1 vi
List of Tables
TABLE 1. Detection limits for the APO-GEM for various

metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
TABLE 2. Relative accuracy of DIAL Air-ICP data . . . . . . . . . . . . 10
TABLE 3. Major anions present in select Hanford Tanks
(in ppm). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
TABLE 4. Comparison of solid phase species observed
in simulation with core sample analysis of Person . . . . . 46
TABLE 5. Solid phase species distribution - 2M NaOH
addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
TABLE 6. Additional simulation results for the 2M NaOH
addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
TABLE 7. Lessons learned (preliminary). . . . . . . . . . . . . . . . . . . . . 87
DIAL 40395-1 vii

Abstract
The Diagnostic Instrumentation and Analysis Laboratory (DIAL), an

interdisciplinary research department in the College of Engineering at
Mississippi State University (MSU), is under contract with the U. S.
Department of Energy (DOE) to develop and apply advanced diag-
nostic instrumentation and analysis techniques to aid in solving
DOE’s environmental management and nuclear waste problems. The
program is a comprehensive effort which includes five focus areas:
• Verification monitors for thermal treatment;
• Deactivation and decommissioning technology support;
• Technical data to support cleanup decisions;
• Product acceptance support;
• Advanced cleanup support - robust immobilization devices.
As part of this program, diagnostic methods are developed and evalu-

ated for characterization, monitoring and process control. The mea-
sured parameters are used to improve, optimize and control the
operation of the overall treatment process.
Moreover, on-site field measurements at various DOE facilities are

carried out to aid in the rapid demonstration and implementation of
modern fieldable diagnostic methods. Such efforts also provide a
basis for technology transfer.
DIAL 40395-1 1
Abstract
In addition to the diagnostic instrumentation development efforts,

DIAL is engaged in the operation of plasma torch facilities. These
facilities are used for both process development and instrumentation
verification. Significant effort is also directed towards the improve-
ment of plasma torches by extending electrode lifetimes.
DIAL 40395-1 2
TASK 1 Verification Monitors for Thermal Treatment
Subtask 1.1. Monitors for Thermal Processes
Thermal treatment processes (incinerators, melters) typically emit

toxic metals (esp. mercury), volatile and semi-volatile organic materi-
als (esp. dioxins and furans), and particulate matter during process-
ing. While the levels from DOE facilities meet current regulatory
limits, the EPA is in the process of promulgating new rules (the so-
called “MACT” rules) with much lower limits. Based on limited test
data, some of DOE’s thermal treatment facilities will require continu-
ous emissions monitoring of process effluents in order to comply with
this rule. Currently, several such monitors are under development,
but, as yet, there are no accepted monitors for this use.
During the first year of the Cooperative Agreement, DIAL will

test monitors for toxic metal effluents in its combustion test facility.
DIAL will contact users, developers, and other stakeholders, and with
their assistance develop detailed test specifications for toxic metals
monitors. Monitors will be brought to DIAL’s test beds for extended
testing. At the completion of testing, a report will be drafted,
reviewed by all parties, revised and issued. This report will detail the
results of testing, and compare the performance of each of the moni-
tors against the specifications.
DIAL 40395-1 3
Task 1. Verification Monitors for Thermal Treatment
Personnel from the major thermal treatment process operators in

the DOE complex (the TSCA incinerator at Oak Ridge, the CIF at
Savannah River, the WERF at Idaho, and the DWPF at Savannah
River) will assist in developing specifications for CEMs, and in
reviewing test plans and test results. DIAL will utilize DOE’s Ad Hoc
CEM group to guide testing and review test results, as well as the
Mixed Waste Focus Area. DIAL will also test the ability of the CEMs
to act as process monitors.
The objective of this subtask is to determine, through testing,

whether existing CEMs meet DOE user specifications.
Air Plasma Off-gas Emission Monitor (APO-GEM)

George P. Miller
Introduction
Project Significance
Increasing regulatory demands requiring significant reductions in

the emission of hazardous air pollutants have led to the need for tech-
niques capable of providing real time monitoring, at the stack, of
toxic metals in combustion gas streams. These waste streams range
from coal-fired boilers and municipal waste combustors to plasma
vitrification systems used for the remediation of low level radioactive
waste. This lack of a fieldable continuous emission metal monitor
(CEM) and process monitor (PM) has been recognized as a signifi-
cant gap in the available technology. The system described below has
been designed to fill this gap.
DIAL 40395-1 4
Background
Over the last twenty years, the use of argon ICP-AES for the mea-
surement of trace elements in solution has matured into a standard
analytical technique. However, unlike the laboratory ICP, it is essen-
tial for a CEM that the system be hardened sufficiently to handle the
problems of a real world environment. These problems include the
ability to readily tolerate the introduction of a variety of molecular
gas matrices, significant variations in moisture and particle loading,
as well as the thermal, vibrational and clogging problems found out-
side the laboratory. The system under development at DIAL has taken
the advantages inherent in inductively-coupled plasma technology
and incorporated them into the APO-GEM - a CEM capable of toler-
ating the real world environment while accurately measuring the real
time concentration of metals in exhaust stacks. Although the APO-
GEM provides significant reduction in operating costs, the main
advantages of the air plasma lie in its increased tolerance to molecu-
lar gases, particle loading and reduced susceptibility to moisture con-
tent (due to more efficient heat transfer from the air plasma to the
sample). On the other hand, it requires higher rf powers, and the max-
imum available ionization energy is reduced from that available in an
argon plasma.
The introduction of exhaust gases into the air plasma results in a

considerably more complex spectra from the line spectra seen in an
argon plasma. The emission spectra includes numerous molecular
bands (e.g., OH, CN, NO, N2+) in the wavelength regions of interest
(200 - 350 nm). This increase in interferences places stringent
requirements on both the resolution of the detection system and the
software used to analysis the data. We are developing two separate
approaches to address these problems: a unique chemometric soft-
ware package to handle the analysis, and an ongoing collaboration
with Ames National Laboratory to reduce the size of the detection
system while increasing the resolution.
DIAL 40395-1 5
The remaining hardware required to complete the system consists

of an isokinetic sampling interface between the APO-GEM and the
exhaust duct. The extractive sampling techniques used introduce the
sample stream into a controlled environment where matrix effects are
minimized and the plasma properties are stabilized. Calibration is
handled by a unique system which mixes calibration standards with
the combustion stream via the isokinetic sampling apparatus. This
effectively compensates for any remaining matrix effects, options that
are impossible for in-stack methods.
Methodology
The APO-GEM system incorporates a novel 3.5-kW solid-state

27.12-MHz rf generator with the load coil modified for air-plasma
operation. This is coupled to a detection system with the off-gas sam-
ple being extracted from the duct and introduced into the air plasma
via an isokinetic sampling system. Figure 1 is a schematic diagram of
the APO-GEM continuous emission monitor.
DETECTOR AIR-PLASMA ISOKINETIC

CCD SAMPLER
CONTROLLER rf POWER NEBULIZER
AIR
COMPRESSOR
A
R
G
O
N
COMPUTER
FIGURE 1. Schematic of APO-GEM continuous emission monitor.
DIAL 40395-1 6
The APO-GEM plasma is started using argon and progressively

switched over to air. Calibration is performed using an ultrasonic neb-
ulizer. The detection system uses a 1-m monochromator and a CCD
detector. This remains the largest single component of the system. It
has adequate resolution, but operates sequentially and is relatively
large. It, nevertheless, provides the ideal platform for identifying and
characterizing the spectral emissions and possible interferences aris-
ing from unidentified components making up exhaust gas emissions.
(To provide simultaneous metal concentration measurements, this
monochromator could be replaced by a polychromator.)
In addition, we are evaluating a novel solid-state spectrometer

developed for this project by Dr. David Baldwin, Ames National Lab-
oratory. This instrument is compact, thermally and vibrationally sta-
ble. It uses a combination of an acousto-optic tunable filter and an
echelle grating to provide the resolution of a 1.5-m monochromator
into a 10-kg package. The successful combination of the solid-state
APO-GEM and this spectrometer represents a large step forward in
instrument development and will reduce the overall size and weight
of the complete package substantially (from original ~1000 kg,
present 250 kg, to ~150 kg) while improving the resolution and
thereby the detection limits.
Isokinetic sampling system. To correctly measure the concentration

of metals present within an exhaust gas stream, it is necessary to
introduce a sample from the exhaust gas stream into the ICP under
isokinetic conditions. Therefore, a sampling system has been
designed to extract such a sample from a gas stream and introduce it
into the air plasma for analysis. The system operates by filling a loop
with sample gas, then pushing this sample with air into the plasma.
The robustness of the air plasma permits an optimum sample flow
rate into the ICP of 1.14 sl/min, approximately three times more than
tolerated by an argon plasma.
DIAL 40395-1 7
Calibration. An important concern with any CEM is the question

of calibration. In this instance, instrument calibration follows a modi-
fied standard ICP calibration procedure.1 An ultrasonic nebulizer is
used to provide metal-containing aerosols at known concentration
(µg/m3). This concentration is determined from
C s uε
C A = -----------
-, (EQ 1)
F
where CA is the aerosol concentration (x 103 µg/m3), Cs is the stan-

dard solution concentration (µg/gsolv), u is the solution uptake to the
ultrasonic nebulizer, F is the air flow rate to the plasma, and ε is the
nebulizer efficiency. The efficiency of the nebulizer was determined
both in the laboratory and again on-site prior to the test. For the initial
instrument calibration, the metal aerosol is mixed with ambient air.
Instrument response was checked against standard calibration curves
prepared previously. In the field, the presence of fly ash as well as
variations in loading and exhaust gas composition allow the possibil-
ity of substantial matrix effects significantly impacting the results of
any real world analysis. This variation in composition between labo-
ratory air and the exhaust gas composition renders any direct compar-
ison of the laboratory air calibrations to the instrument off-gas
response highly suspect. To circumvent this problem, we have devel-
oped a novel technique whereby the calibration standards are mixed
with the exhaust off-gas at the entrance to the sampling loop while
maintaining isokinetic conditions. This ensures that the standard and
off-gas samples are matrix-matched. This allows recalibration and
QA checks to be performed on-line under actual operating condi-
tions.
To further improve the sensitivity of the instrument, a novel

chemometric software package has been developed which by model-
ing background spectrum (at the spectra regions of interest) effec-
tively reduces the background noise and thus improves the instrument
sensitivity. To apply this method accurately, data from the spectral
DIAL 40395-1 8
regions of interest was collected during the shakedown period prior to

the test. In addition, as the instrument presently employs a sequential
detection system, wavelength calibration is essential. A chemometric-
based software package was developed to check and, if necessary,
correct wavelength calibration. This software checks the wavelength
position with respect to the pixel position on the CCD every time the
wavelength setting is changed as well as periodically checking for
instrument drift.
Detection limits. The toxic metal species of concern to EPA and

DOE include: As, Be, Cd, Cr, Hg, Sb, Pb. The present detection limits
for a number of metals are given in Table 1. Further improvements in
sensitivity are required to meet the expected emission limits.
TABLE 1. Detection
limits for the
APO-GEM for various metals.
Metal Detection Limits

Instrument (mg/sdcm)
As 47
Be 0.07
Cd 2.5
Co 0.6
Cr 0.25
Hg 20
Mg 0.05
Ni 0.4
Pb 0.9
Sb 55
Sr 0.003
DIAL 40395-1 9
TABLE 2. Relative accuracy of DIAL Air-ICP data.
Be Cd Cr Hg Pb
RM 1 to 10 40% 26% 40% 13% 21%
RM 11 to 20 43% 46% 59% 67% 42%
Metal concentrations and relative accuracy. The

DOE/EPA demon-
stration at Raleigh was the first opportunity to check the accuracy and
quality of the data provided by the APO-GEM. The relative errors
with respect to EPA Method 29 are given in Table 2. Three of the five
metals are within 30% for the high concentration level (75 µg/dscm).
None are within that range at the low concentration level (15 µg/
dscm). These results are excellent considering the uncertainty present
in the RM data at these low levels.
Work Accomplished
Results and Discussion
The field trip late last year to participate in the DOE/EPA-spon-

sored demonstration at Raleigh, NC was the instrument’s first field
trip and its first long test run. It amply demonstrated the technique’s
potential as a CEM and as a process monitor both in terms of robust-
ness and results. As was expected, the field trip served well as a
shakedown. A number of possible improvements were noted and are
being implemented. These improvements are relatively minor com-
pared to the areas of research that remain to be addressed (see below).
Research Progress
Progress this quarter has been hampered with the move into the
new building. In addition, the loss of Dr. Zhu (without replacement)
has had a significant impact on progress. However, a certain amount
of progress has been made. In particular:
DIAL 40395-1 10
Air plasma parameters. A laboratory study characterizing the

effects of moisture on the air plasma’s properties has been performed
(see Figure 2), and a publication is in preparation.
Chamber temperature effect on Mg II/Mg I

1
0.70
1.75
0.60 2.5
0.50 3.25
4
0.40 4.75
0.30 5.5
6.25
0.20 7
0.10 7.75
8.5
0.00
9.25
140 78 63 53 49 44
10
Chamber Temperature 10.75
Chamber temperature effect on Mg II/Mg I

1
0.70
1.75
0.60 2.5
0.50 3.25
4
0.40 4.75
0.30 5.5
6.25
0.20 7
0.10 7.75
8.5
0.00
9.25
140 78 63 53 49 44
10
Chamber temperature effect on Mg II emission
12 1
1.75
10 2.5
3.25
8
4
6 4.75
5.5
4 6.25
7
2
7.75
0 8.5
140 78 63 53 49 44 9.25
10
FIGURE 2.The effect of moisture on the emission of Mg in an

air-plasma. (140 corresponds to dry, 49 to saturated flows).
DIAL 40395-1 11
Sampling interface. Modifications to the isokinetic sampling system

are in progress
An evaluation of high resolution AOTF-echelle

Detection System.
spectrometer in collaboration with Ames National Laboratory.
A week-long test of this instrument occurred at DIAL in August

1998. The result of these experiments indicated that significant
progress has been achieved over the earlier AOTF-FP spectrometer,
and a decision was made to use this instrument to eventually replace
the 1-m monochromator. This will provide a substantial reduction in
overall instrument size.
A paper was presented at the ACS 215th national meeting, Dallas,

March - April, 1998, entitled “High-resolution interferometric spec-
trometer for continuous emission monitoring” by D. P. Baldwin, D. S.
Zamzow and G. P. Miller. Abstracts were submitted to both the
FACSS and Gaseous Electronic Conferences which are scheduled for
October 1998.
a) b)
Intensity (arb. units)
Intensity (arb. units)
228.76 228.80 228.84 309.95 310.00 310.05 310.10

Wavelength (nm) Wavelength (nm)
FIGURE 3. ICP emission spectra obtained using the AOTF-echelle

spectrometer, illustrating the resolution of the system: (a) Cd (I) 228.802 and
As (I) 228.812 nm emission-lines are nearly baseline-resolved; emission lines
for Fe (I) at 309.990, 309.997, 310.030, and 310.067 nm are shown in (b).1
DIAL 40395-1 12
Work Planned
A 75% reduction in available manpower hours will continue to

make a significant impact on progress as will delays due to the move
into the new building (off-gas system inoperable). While progress has
been made, considerable research remains. Areas to focus on include:
Air Plasma Parameters
A study of the following real world effects on the properties of the

air plasma need to be understood and accounted for:
•moisture - dry to saturated,
•particle loading - size,
•interferences.
Sampling Interface
Further research on potential losses within the isokinetic system

under sampling conditions ranging from dry (static) to saturated is
essential. The impact of long term, real world effects (e.g., clogging,
vibration, thermal effects) also remains to be studied.
Calibration
Our novel method of spiking the combustion stream as it is sam-

pled has the potential of solving the CEM calibration problem. How-
ever, significant research remains to be done to validate this
assumption. Experiments will be performed to measure the accuracy
and repeatability of the technique.
Detection System
Monochromator-based system. The software package needs to be

rewritten taking into account the lessons learned at the North Caro-
DIAL 40395-1 13
lina test. Enhancements in the modeling package can be made to fur-

ther improve signal-to-noise, i.e., detection limits.
High resolution AOTF-echelle spectrometer. Significant progress has

been achieved and the instrument is expected to eventually replace
the 1-m monochromator. However, a number of improvements are
required to harden the instrument to withstand a real world environ-
ment.
Reduced-pressure Air-ICP (Ames Laboratory)
The milestone for this project involves testing the hardware on the
DIAL test stand in August 1999. Preparations and modifications nec-
essary for this test will be established during the next quarter.
The other areas to be addressed in the next quarter will depend on

both manpower limitations and availability of the off-gas test stand.
Reference
1. Baldwin, D.P., Miller, G. and Zamzow, D.S., November 1998. AOTF-

Echelle Spectrometer for Air-ICPAES Continuous Emission Monitoring of
Heavy Metals and Actinides. Proceedings of the SPIE Technical Confer-
ence, 3534:59.
Laser-induced Breakdown Spectroscopy

J. P. Singh, F. Y. Yueh and H. Zhang
Introduction
Toxic metal emissions from various waste processing off-gas sys-

tems represent a significant health hazard. This technical task has
been focused on the development and application of laser-induced
DIAL 40395-1 14
breakdown spectroscopy (LIBS) to monitor RCRA metals from ther-

mal treatment processing facilities. LIBS is a laser-based technique.
It applies a high power laser beam to vaporize and excite the sample
in situ in a single step.2,3 This is accomplished by focusing a pulsed
laser beam at the test point to produce a laser-induced plasma. The
plasma atomizes and electronically excites the various atomic species
present in the test volume. The intensities of the atomic emission
lines observed in the LIBS spectrum are used to infer the concentra-
tion of the atomic species. The capability of the LIBS system for real
time metal monitoring was evaluated in various field tests.4-9 The field
test results show the calibration technique of LIBS needs further
improvement to provide accurate quantitative measurement in various
test environments. During this work period, a study of laser energy to
LIBS signal was performed. The results of this study is summarized.
Work Accomplished
LIBS has been evaluated as a near real time measurement tech-

nique for monitoring the concentration of metallic species in the off-
gases from waste processing facilities. To be accepted by EPA as a
CEM, the quantitative figure of merit for LIBS needs to be improved.
Due to the difficulty of injecting a known amount of sample into the
practical gas stream, LIBS calibrations were all performed in the lab-
oratory. How to transfer the LIBS calibration obtained in the labora-
tory to a practical environment is a great challenge for quantitative
LIBS measurement. A series of studies to correlate LIBS background
with the change in excitation condition was conducted. LIBS data
were recorded with different detection windows and laser energies.
Figure 4 shows the variation of the Pb LIBS signal and background at
different laser energies. The background was found to increase as the
laser energy increased. The Pb signal also increased with the laser
energy. However, the Pb signal was almost unchanged after laser
energy went above 180 mJ. This indicates the signal-to-background
ratio (S/B) can be used in LIBS calibration but in limited laser energy
ranges. Figure 5 shows S/B for Pb, Cr, Hg, Cd, and Be at different
DIAL 40395-1 15
laser energies and detection windows. These data are helpful to deter-
mine the best experimental setup for LIBS calibration. Since laser
energy fluctuates from pulse to pulse, the laser energy which give an
S/B change less than 20% in the laser energy fluctuation ranges
should be used in the calibration to improve the precision and accu-
racy of the LIBS measurement.
FIGURE 4. LIBS signal (a) and background (b) as a function

of laser energy.
DIAL 40395-1 16
FIGURE 5. S/B as a function of laser energy. Data were taken at the gate delay/
gate width of (a) 20 µs/5 µs, (b) 25 µs/5 µs, (c)35 µs/5 µs, and (d) 45 µs/5 µs.
The study of LIBS calibration will continue. LIBS calibration

data will be collected at different sample temperatures and ambient
conditions.
References
2. Cremers, D.A. and Radziemski, L.J. 1987. “Laser Plasmas for Chemical
Analysis” in Laser Spectroscopy and its Application, L.J. Radziemski,
R.W. Solarz, J.A. Paisner, eds. New York: Marcel Dekker, Ch. 5, p. 351.
3. Radziemski, L.J. and Cremers, D.A. “Spectrochemical Analysis Using

Plasma Excitation” in Laser Induced Plasmas and Applications, L.J.
Radziemski and D.A. Cremers, eds. New York: Marcel Dekker, Ch. 7, pp.
295-326.
4. Singh, J.P., Yueh, F.Y. and Zhang H. 1997. Process Control and Quality,
10:247.
DIAL 40395-1 17
5. Singh, J.P., Zhang H., Yueh, F.Y. and Carney, K.P. 1996. Applied Spectros-
copy, 50:764.
6. Singh, J.P., Zhang, H. and Yueh, F.Y. February 1996. Transportable Vitrifi-
cation System Shakedown Test, Westinghouse Savannah River Corporation
and Diagnostic Instrumentation and Analysis Laboratory: Laser-induced
Breakdown Spectroscopy Measurements. US DOE Contract No.
DE-FG02-93CH-10575. DIAL 10575 Trip Report 96-1.3.
7. Singh, J.P., Zhang, H. and Yueh, F.Y. April 1996. DOE and EPA Continu-
ous Emission Monitoring Test at EPA National Risk Management Research
Laboratory (NRMRL). US DOE Contract No. DE-FG02-93CH-10575.
DIAL 10575 Trip Report 96-2.
8. Singh, J.P., Zhang, H. and Yueh, F.Y. 1996. Plasma Arc Centrifugal Treat-
ment PACT-6 Slip Stream Test Bed (SSTB) 100-hour Duration Controlled
Emission Demonstration (CED) Test. DIAL Trip Report 96-3.
9. Singh, J.P., Zhang, H. and Yueh, F.Y. September 1997. DOE and EPA Con-
tinuous Emission Monitoring Test at EPA National Risk Management
Research Laboratory (NRMRL). DIAL Trip Report 97-1.
Subtask 1.2. Mercury Absorber Technology
Many of DOE’s low-level wastes contain mercury. If the LLW is

treated by thermal treatment processes such as incineration, the mer-
cury will be emitted to the off-gas system and must be removed.
While the levels from DOE facilities meet current regulatory limits,
the EPA is in the process of promulgating new rules (the so-called
“MACT” rules) with much lower limits. Based on limited test data,
some of DOE’s thermal treatment facilities will be unable to comply
with these rules without significant capital investment.
A mercury removal technology, based on an innovative absorber,

has been developed in Russia and deployed in room temperature
applications there. DIAL will test this absorber because, if it proves
DIAL 40395-1 18
to be effective, its use would require almost no changes to existing

facilities. Key performance characteristics which will determine
whether the absorber can be used in an off-gas system are the maxi-
mum temperature at which it is effective and its capacity. DIAL will
utilize its test stand and off-gas systems to provide this data. The mer-
cury absorber will be installed in the off-gas system. The temperature
of the off-gas hitting the material will be varied and mercury removal
will be monitored. Mercury-laden off-gas will be sent past the
absorber until no further removal of mercury occurs. The maximum
mercury loading will be determined, as well as the maximum temper-
ature at which the material is effective.
Representatives from the Idaho office of DOE, and from the

developer of this innovative technology, will assist in developing test
plans, will observe the tests, and will review test plans and test
results. If initial testing is successful, stakeholders will be notified
(through the Southern States Energy Board and the California EPA)
and invited to participate in further performance testing.
The objective of this subtask is to determine, through testing, the

maximum temperature at which the mercury absorber is effective,
and the maximum loading of the material.
This project has been deferred.
DIAL 40395-1 19
TASK 2 Deactivation and Decommissioning
Technology Support
Subtask 2.1. Pipecleaning Technology

R. Daniel Costley
Introduction
One of the most difficult aspects of D/D of DOE’s existing facili-

ties is dealing with pipes which have carried radioactive solutions.
Current practice is to attempt to flush contamination out of the pipe,
or fix the contamination in the pipe, and then to either leave the pipe
in place or cut it out. Flushing tends to either create more waste, and
generally leaves behind the radioactivity which is trapped in the oxide
layer in the metal. Cutting contaminated pipe creates the potential for
airborne activity. Leaving the pipe in place is sometimes justified, but
in the case of DOE’s separations canyons is not likely to be success-
ful because of the level of activity left behind.
Researchers at Mississippi State University have developed a

technique which uses repetitive high voltage acoustic shock waves in
water to produce acoustic shock waves. Laboratory and field testing
has shown these shock waves to be very effective in removing scale,
silt, and other fluid saturated deposits from the interior walls of steam
condenser and heat exchanger tubes. The debris removed from the
DIAL 40395-1 20
Task 2. Deactivation and Decommissioning Technology Support
walls is then flushed away. This method is a noncontact, nonchemical

method for removing these deposits. A version of this technique has
been demonstrated on heat exchanger piping in an operating nuclear
reactor. However, this was a once-through system which is not opti-
mal from a waste generation standpoint.
DIAL will develop a closed loop system. DIAL will test the sys-
tem on pipes containing simulated contamination in many forms
(e.g., scale, corrosion products, sedimentation). The ability of this
technology to remove obstructions from process piping (e.g.,
WERF’s heat exchangers, or the HLW evaporator at SRS) will also be
investigated. The system will then be demonstrated at Florida Interna-
tional University’s D/D testing facilities to see if it is feasible to use
this system to unclog pipes. In the outyears, a radioactive demonstra-
tion using actual contaminated piping is anticipated. This most likely
will be held at Savannah River.
The objective for this task is complete development of pipeclean-

ing technology, leading up to a radioactive demonstration.
Work Accomplished
A second tube cleaning system is being built at DIAL. The first

was built at the High Voltage Lab at Mississippi State University.
Parts have been procured. A closed loop circulation system is also
being built. The laboratory space has been modified to accommodate
the system. A presentation on this system was made at X’Change 97.
A short video was made as part of this presentation. The video, along
with other materials, has been circulated to several companies and
agencies involved in D&D in an effort to market the technology and
find a commercial partner. We have found a partner willing to collab-
orate on an SBIR type proposal.
DIAL 40395-1 21
Conclusions
The TCS has been successfully demonstrated at Sequoyah

Nuclear Power Plant (TVA) and the Wabash River Coal Fired (Plant
Public Service of Indiana) to clean scale and other deposits from 1 in.
diameter heat-exchanger tubing. This previously developed and dem-
onstrated technology provides an excellent basis for further develop-
ing a system that will decontaminate radiologically contaminated
surfaces. This method appears suitable for cleaning and decontami-
nating tubes, pipes, and other cylindrical storage containers capable
of containing fluids. There are several advantages of this technique
over existing technologies. The primary advantage is that the expo-
sure of workers to hazardous and radioactive materials is minimized.
This is because the cable can be fed through a bushing into the pipe
so that workers do not come into contact with the material within the
pipe. Further, the generation of secondary waste is minimized, or
avoided. The water in the pipes transports the scale out of the pipes.
This same water can be reused to clean other pipes after the foreign
matter has been separated from it using conventional means (filtra-
tion, centrifuge, settling). Since deposits are knocked off the surface
of the pipe through its interaction with the acoustic wave, the use of
brushes or chemicals is avoided, further reducing the generation of
secondary wastes.
Work Planned
A new, improved pulsed acoustic pipe cleaner will be completed

at DIAL. This new system will be more robust and have several
improved features. We will also finish the assembly of the closed loop
circulation system. Pipes with different types of fouling will be
cleaned in this system in order to determine the effectiveness of the
TCS for different applications. We will continue to seek an on-site
demonstration at a DOE facility.
DIAL 40395-1 22
References
10. Costley, R.D., Mazzola, M.S., and Grothaus, M.G. December 1997.
Pulsed Acoustical Technique for Decontamination of Piping and Contain-
ment Systems. Presented at X-Change’97: The Global D&D Marketplace,
Miami, FL.
11. Mazzola, M.S., Grothaus, M.G., Walch, M., and Jones-Meehan, J. July
1995. New Electrical Control Methods to Prevent Power Plant Fouling.
Tenth IEEE Pulsed Power Conference, Albuquerque, NM.
Subtask 2.2. Wall Removal Monitor

Mark Henderson and R. Daniel Costley
Introduction
DOE will generally use private vendors to D/D its existing facili-
ties. A key to the success of this privatization approach is finding a
method capable of providing near real time feedback on the removal
of contaminated material. This will allow the vendor to make deci-
sions while crews are still deployed about the status of removal of
contamination, and allow DOE to make informed decisions about
payment of the vendor.
DIAL has developed an approach based on Fourier transform pro-

filometry which appears to at least partially fulfill this need. This
technique uses the Fourier transform of an image of a surface to pro-
vide depth information. Thus, for removal of contaminated concrete
from a wall, the technique can provide depth information for the
entire wall relative to a starting point.
DIAL will first automate the process of image capture and pro-
cessing, so that it can be done in the field with minimal operator inter-
DIAL 40395-1 23
vention. The automated operation of the equipment will then be

demonstrated at DIAL. A demonstration of the system as part of a D/
D operation will be conducted at the D/D test bed which has been
established by Florida International University. A radioactive demon-
stration of the technique will be sought at the Fernald site. The same
technology potentially can also be deployed as part of the Hanford
Canyon Initiative.
The objective of this task is to develop and deploy a technique to

monitor the rate and uniformity of removal of contaminated concrete
walls.
Work Accomplished
An acoustic ceiling tile, which had random, dark flecks, was used
as the test object (ceiling tile is easily modified with a knife). A rail,
which sits on two tripods, was constructed to hold the camera and the
projector. Tests were done on the “noisy” tile by gauging holes and
sections from the tile using a knife and measuring the amount of
material removed both by using FTP and a caliper (for reference see
the DIAL technical memo on the Wall Removal Monitor which
includes several images). The camera used in these tests was a com-
mercial home video camera. The spatial resolution (the distance
between points on the surface) depends on the area of the surface
being imaged and the resolution of surface variation. As a result the
finished profile map can be referenced to the original surface and only
the things that are different show up in the report. A third enhance-
ment to FTP has been developed to allow information to be collected
at multiple resolving abilities concurrently. The technique uses two
patterns that are projected onto the surface at the same time so that
they overlap. This allows both the global picture to be seen along with
the details, and prevents “forest-for-the-trees” problems that can
occur.
DIAL 40395-1 24
Conclusions
A system has been demonstrated that can accurately measure

large areas with a high degree of precision on “noisy” surfaces. The
system has been constructed for fieldwork and uses commercial parts.
All necessary field measurements are quick and easy to make, and
processing is in near real time. FTP fits the role of wall removal mon-
itor well, as it can measure a surface profile relative to the original
surface. From the depth information gathered using FTP it is possible
to calculate volume of material removed, average depth of material
removed, and point-wise depth of removal. The system can be used at
the job site potentially saving the contractor and the contracting
agency time and money by preventing costly re-visits and ensuring
quality.
Work Planned
A demonstration of this technology is scheduled for December

1998 at the test facility at HCET-FIU. Modifications will be made to
the configuration so that floors, ceilings, and other surfaces can be
monitored. A commercial partner will be sought to commercialize the
technology for this application.
Reference
12. Henderson, M.E. and Costley, R.D. Wall Removal Monitor. DIAL Techni-
cal Memo WRM 1198.
DIAL 40395-1 25
TASK 3 Technical Data to Support Cleanup Decisions
Subtask 3.1. Dioxins/Furans in Incinerator

Burner
Thermal treatment processes (incinerators, melters) typically emit

toxic metals (esp. mercury), volatile and semi-volatile organic materi-
als (esp. dioxins and furans), and particulate matter during process-
ing. While the levels from DOE facilities meet current regulatory
limits, the EPA is in the process of promulgating new rules (the so-
called “MACT” rules) with much lower limits. As was discussed at
the National Technical Working Group “pre-meeting” on November
4, 1997, preliminary data indicate that the Consolidated Incinerator
Facility at SRS may not be able to meet the very stringent MACT
rules for dioxin. Based on preliminary testing, Savannah River per-
sonnel suspect that the fuel oil burner used in the incinerator may be
an important contributor to the problem.
Installing additional control devices on the CIF would be expen-

sive, and difficult to accomplish in a radioactive environment. As a
result, SRS and the other DOE incinerator operators require addi-
tional testing to confirm that the incinerator’s burner is the source of
the dioxins/furans. DIAL will expand the scope of testing to be per-
formed for a commercial burner manufacturer to include determina-
tion of the concentration of dioxins/furans produced as a function of
DIAL 40395-1 26
Task 3. Technical Data to Support Cleanup Decisions
burner operating conditions. DIAL will take its instrumentation to the

burner manufacturer. Dioxin/furan contents in the effluents will be
determined as a function of burner operating conditions. As a result,
DIAL may be able to provide a window of burner operating condi-
tions which could avoid the need for additional control devices.
An engineer from DOE’s Consolidated Incinerator Facility will

work with DIAL on this effort. He will assist by ensuring that testing
adequately reflects conditions in the CIF, and by reviewing test plans
and test reports.
The objective of this task is to determine dioxin/furan production

from a fuel oil burner.
Dioxin Tests
John Etheridge
Introduction
Because of the concern over dioxin production in mixed waste

and municipal solid waste incinerators, there is a great need for more
definitive data concerning the affects of incinerator operating condi-
tions of on the production and destruction of dioxins and furans.
Although there is a substantial quantity of data available, it is derived
mostly from laboratory scale combustion systems that may be too
small for the data to be meaningfully applied to full scale incinerators
and from operating incinerators where precise control of the system
parameters and repeatability of results are both problematic. DIAL’s
combustion test stand is large enough to produce data that is applica-
ble to full scale incinerators, is highly controlled, and is capable of
producing very repeatable operating conditions.
DIAL 40395-1 27
Work Accomplished
A series of tests using DIAL’s combustion test stand have been

designed to produce data that should provide insight into the condi-
tions with produce dioxins. A sampling system which is both isoki-
netic and isothermal has been designed for sampling of both
particulate bound and gas-phase dioxins. A test section which is eight
feet in length has been designed for this series of tests. The test sec-
tion will provide a nearly constant temperature for its entire length.
The combustion test stand is being reconfigured to produce tem-

peratures that can be varied from 300 to 700 F in the test section that
was specifically designed for these tests. In order to provide this
range of temperatures without changing the combustion conditions,
retractable single loop water cooled heat exchangers will be used at
several locations in the high temperature sections of the test stand in
order to temper the gas stream. This technique for producing a range
of lower temperatures should minimize the chance of produce dioxins
in the heat exchanger due to local cooling of the gas stream to the
temperature at which they are formed. At present the channel and the
combustor section of the test stand are in place.
Work Planned
The air pollution control system and fuel tank will be moved to
the new test facility at about mid-November. Installation of the con-
trol and monitoring system will begin at that time.
The first tests should begin during the first half of December. The
combustion test stand will be fired with natural gas for the first series
of tests and then the series will be repeated with fuel oil No. 1.
DIAL 40395-1 28
Testing planned is intended to add insight into the dependence of

dioxin/furan concentrations on both temperature and metal content of
the ash, off-gas chemistry, and SO2 concentrations in the off-gas.
Detection of Chlorinated Organics

by Cavity Ring-down Spectroscopy
Ram Vasudev and William Dunsford
Introduction
The goal of this project is to develop a sensitive real time probe

for chlorinated volatile/semi-volatile organic compounds (VOC/
SVOC). The need for such a detector is especially urgent in the case
of SVOCs such as dioxin characterized as being among the most
toxic man-made chemicals.13 We are exploring the technique of cav-
ity ring-down spectroscopy (CRDS) for this purpose.14,15 Traditional
laser techniques such as resonance-enhanced multiphoton ionization
(REMPI) and laser-induced fluorescence (LIF) are not very suitable
for chlorinated aromatics because of fast excited-state intersystem
crossing (ISC) in these molecules.16 CRDS, by comparison, is not
influenced by excited-state photophysics because it is solely absorp-
tion-based and is thus a perfectly general technique. It is also superior
to conventional methods such as FTIR spectroscopy because it is
more sensitive and optoacoustic spectroscopy because it can provide
absolute absorption cross-section. It is thus a very promising univer-
sal toxic gas detector.
The experimental setup for cavity ring-down spectroscopy has

been described previously14,15 and will not be repeated here in detail.
Briefly, the absorption pathlength of a pulsed laser through an absorb-
ing sample is made very long by trapping the pulse between the mir-
rors of a high-finesse (low-loss) confocal/semi-confocal optical
DIAL 40395-1 29
cavity containing the sample. The effective pathlength in suitable

cases can be several kilometers, so very small concentrations of
chemical species can be detected, being limited predominantly by
scattering losses and cavity mirror reflectivity. The absorption coeffi-
cient of an absorber is obtained by analyzing the time-decay profile
(the “ring-down” waveform) of the light transmitted by the cavity.
Work Accomplished
Considerable difficulties have been encountered because of lack

of infrastructure in DIAL’s new building. In spite of the hardships,
progress has been made in the detection of chlorinated VOCs. In
these studies, we have exploited the accidental coincidence of the
fourth harmonic (266 nm) of an Nd:YAG laser with a weak absorp-
tion feature of each VOC. Linear relationship is found between
absorber concentration and CRDS signal, as shown in the example in
Figure 6. The inferred detection limit (DL) is in the parts-per-million
range. This can be improved considerably because the fixed wave-
length (266 nm) used in these experiments overlaps with rather weak
absorption features in the spectra of these molecules. In addition, the
cavity mirrors used in these studies are rather cheap/substandard
(with reflectivities, R, of ~ 0.980 - 0.997), and the cavity is somewhat
short (23.8 cm). With improvements in these parameters, the sensitiv-
ity is expected to improve significantly, to the parts-per-billion range
in suitable cases. However, we note that even the DL achieved here
should be good enough for detecting VOCs at concentrations found
in, for example, landfills.17
The most significant aspect of this work is the ease with which
chlorinated VOCs can be detected by CRDS. In addition, the DL is
unaffected by the extent and site of chlorination. In this respect
CRDS is superior to methods such as LIF and REMPI that are influ-
enced by excited-state nonradiative decay induced by the presence of
chlorine.
DIAL 40395-1 30
FIGURE 6. Results for 1,4-dichlorobenzene. Shown here is the

inverse of cavity ring-down time τ (proportional to absorption)
at 266 nm as a function of pressure of 1,4-dichlorobenzene.
The error in pressure measurements is ~2-3 mTorr.
Work Planned
Work will continue with a variety of chlorinated aromatics, espe-

cially those that are good surrogates for dioxin. It will include:
•acquiring high-quality spectra for these molecules, and
•improving the detection limits through improvements in the
experimental setup, as stated previously.
References
13. I.K. Puri (ed.) 1993. Environmental Implications of Combustion Pro-

cesses. Boca Raton: CRC Press.
DIAL 40395-1 31
14. J.J. Scherer, J.B. Paul, A. O’Keefe and R.J. Saykally. 1997. Chem. Rev.
97:25 and references therein.
15. R. Vasudev, et al. July 1998. Application of Modern Diagnostic Methods to

Environmental Improvement. DIAL 10575, Final Report.
16. E.C.Lim (ed.) 1974. Excited States, Vol. 1. New York: Academic Press;
J.R. Birks. 1970. Photophysics of Aromatics Molecules. New York: Wiley-
Interscience.
17. B. Eklund, E.P. Anderson, B.L. Walker and D.B. Burrows. 1998. Environ.
Sci. Technol. 32:2233.
Subtask 3.2. Dissolution of Hanford Salt

J. S. Lindner and R. K. Toghiani
Introduction
Project Significance
The Tank Waste Remediation System (TWRS) is responsible for

pretreating the legacy wastes contained in the double and single-shell
tanks at Hanford and delivering these streams to the privatization
contractor, British Nuclear Fuels Limited. The stored wastes contain
three discernible constituents, high ionic strength liquid, sludge, and
saltcake. Most of the experimental and theoretical modeling efforts to
date have been concerned with the sludge and liquid fractions; how-
ever, a large portion of the waste, estimated to be 60% by mass in
some tanks, exists as saltcake. Recognizing this deficiency, the Tank
Focus Area (TFA) issued Technical Response 671:PBSTW05.
The work described here is a result of a successful proposal

funded by TFA with cost sharing from DIAL.
DIAL 40395-1 32
Thermodynamic modeling of complex, multi-component electro-

lyte solutions at high ionic strengths and with proper consideration of
solids formation is a formidable task. Workers evaluating the waste at
Hanford have selected, based on initial comparisons between experi-
mental results and an assessment of available software, the Environ-
mental Simulation Program (ESP, OLI Inc.). The code has
subsequently been used for modeling laboratory sludge leaching
experiments and tank contents.18-20 To our knowledge, the work
reported here is the first application of the model to saltcakes. The
short time period in which ESP has been in use at Hanford suggests,
however, that evaluation of the code for different applications is an
evolving process. Thus, the work performed here is implicitly cen-
tered on model validation.
All of the work connected with this subtask has been aimed at
providing end-users at Hanford with additional information regarding
the performance of the ESP code. A main goal of the work is to
increase confidence in the predictive capability of the model. A
proven, validated process engineering tool could result in consider-
able cost savings. For example, proper modeling of the pretreated
waste will indicate the propensity of the waste to foul transfer lines;
thereby eliminating the high costs of effecting repairs and slipped
delivery schedules. In addition, analytical characterization of the
large volume of waste at the site, (55 million gallons) along with the
process streams that will be generated upon retrieval of the waste, is
impractical. A tool is needed which can describe the waste and asso-
ciated process streams with sufficient reliability such that costly char-
acterization studies can be minimized.
Background
The previous work at Hanford has indicated some limitations in

the application of ESP.18-20 Solid-liquid equilibrium (SLE) model cal-
culations have been found to agree with laboratory results for aque-
ous solutions containing most of the pertinent single salts (NaCl,
DIAL 40395-1 33
Na2C2O4, NaNO3, etc.). At elevated ionic strengths, however, the sol-

ubilities predicted by the model are less than experimental observa-
tions. Consequently, the code predicts higher solids loadings and this
has potential ramifications on the privatization contract through the
amounts and types of diluents used for pretreating the waste.
Other questions regarding the code concern the quality of the data
used in the integral software databases, Analytical results on the tank
wastes at Hanford have indicated the presence of a number of double
salts such as, Na-F-PO4, Na-F-SO4, and Na-SO4-CO3.21 Literature
data on these systems are rare. What results are available indicate that
various types of solids structures, crystals and gels, can result
depending on composition. Natrophosphate, Na7F(PO4)2.19H2O, for
example, has been observed to form gels.22,23 Sodium phosphate
Na3PO4.XH2O can form different crystal structures depending on the
extent of hydration. Accurate modeling of the partitioning of the sol-
ids and liquid phase constituents will only be as good as the funda-
mental data used in the model.
Methodology
Some identified options for validating the ESP code include:

•comparisons to experimental data on actual tank samples;
• determination of the SLE behavior for those systems which
are of direct importance to the end-users at Hanford and
where literature results are fragmentary;
•comparison of the results of the model to other thermody-
namic models; and
•examination of the thermodynamic data called by the code.
Little is known about the pretreatment requirements of saltcakes

and experimental studies on this portion of the waste are lacking. An
evaluation of the predictive capabilities of the ESP model is possible
by comparing code predictions with the results of experimental stud-
DIAL 40395-1 34
ies. Other comparisons of the model to tank sample analysis include

direct customer requests.
Critical evaluation of the fundamental thermodynamic constants

called by the model permit an assessment of the quality of the data
used by OLI Inc. and can identify possible error sources. In many
instances, especially with regard to the double salts systems cited
above, sufficient data does not exist in the literature and any compila-
tion will only consider the available information as estimates. Deter-
mination of the solubilities and associated phase diagrams for
selected systems provides a means for ensuring the quality of the
experimental data and a path for model sensitivity calculation.
Different theoretical representations can be used to calculate the

SLE behavior of aqueous systems. Comparison of the results from
ESP with other thermodynamic models allows an independent check
on the thermodynamic framework used and may also indicate defi-
ciencies in the ESP model or associated database.
Work Accomplished
Results
Progress made in the four project areas has previously been

reported to TFA.22 Two letter reports on the application of ESP to dis-
solution of the crust present in Hanford tank 241-SY-101 have also
been distributed.23,24 Highlights of these efforts are given below.
Additional information on these studies is available in the cited refer-
ences.
The work scope of the last half of FY 98 concerned evaluation of

the fundamental data in the ESP databases, validation, and use of an
instrument capable of measuring solubilities, a comparison of ESP
predictions with those from the SOLGASMIX model for natrophos-
DIAL 40395-1 35
phate, modeling of saltcakes from three Hanford tanks, and extensive

studies on SY-101.
Fundamental data called by ESP. The prediction of solid-liquid equi-

librium by ESP is only as accurate as the fundamental thermody-
namic constants called by the software. To this end, the program
contains, in specific application databases, extensive listings of the
constants for many inorganic and organic constituents. The heteroge-
neity of the elemental constituents in the Hanford feed implies a con-
siderable number of possibilities with regard to molecules that can be
formed. Consequently, the quality of the data is critical with regard to
properly describing the waste that will be encountered.
Evaluation of the data was centered on the comparison of the

enthalpy of formation, Gibbs free energy of formation, standard state
entropy at 298 K, and heat capacity. Sources for the data included the
ESP public and private databases, NIST, CODATA and NES.25-27 The
constants in the NIST and CODATA compilations have been criti-
cally reviewed. A majority of all of the results available is collected in
the NEA listings.
The data search engine (periodic table function) within ESP was
used to select the molecules and ions for comparison. Elements that
are present in large quantities in the waste at the site include H, Na,
Al, N, O, N, S, P, and F. The inclusion of other systems containing Si
and Cl are currently in progress. All of the data from the different
sources were collected in a spreadsheet. The NIST and CODATA val-
ues were treated as confirmed, whereas, the constants given in the
NEA database were subjected to a statistical calculation. If a particu-
lar value within the given NEA set was found to be outside of ± 2
standard deviations of the mean, that value was omitted and a new
calculation performed.
Tables of the fundamental constants and the relative errors of

these values between the different data sources are collected in Ref.
DIAL 40395-1 36
23. In summary, the data from all of the sources was very similar for
the Gibbs free energy of formation and the enthalpy of formation.
Ratios in ∆G˚F and ∆H˚F were calculated for all of the entries at 99.93
± 1.8 and 99.72 ± 1.6 kJ/mol. Errors in the standard state entropy and
heat capacity were larger for systems containing fluorine; AlFx, HF,
and NaF. If these molecules and ions are omitted, the average differ-
ence between the ESP values and the other data bases for S0298 was
calculated as 97.1 ± 19.9 J/mol K. Data for the heat capacities, where
available, also exhibit considerable scatter.
Although additional data comparisons are needed, especially with

regard to the aluminosilicate system, it appears that a short-term
examination of the fundamental constants called by ESP can be used
to identify potential discrepancies with reported literature data. The
apparent errors in the constants for fluoride containing systems, such
as NaF, which is a common molecule observed in laboratory analysis
of Hanford wastes, are also being addressed in the experimental stud-
ies of this project.
Experimental solubility determinations. As

noted above, only limited
results have been cited for many of the double salt systems present in
the site holdings. Determination of solubilities at different solution
conditions, pH, ionic strength and temperature, provides one method
for direct comparison to the ESP model. Such measurements can be
performed under isobaric (constant pressure) conditions, or by capi-
talizing on changes in the system refractive index, which occur at the
SLE point.28,29 Experiments at constant pressure require considerable
control during the lengthy duration’s needed to achieve equilibrium.
Consequently, the initial choice in developing an experimental appa-
ratus was to perform the measurements based on the refractive index
or Tyndall effect.29
A block diagram of the instrument is given in Figure 7. The sam-

ple cell is a glass-jacketed reactor flask that is connected to a circulat-
ing water bath. The top of the cell was machined from poly(oxy-
DIAL 40395-1 37
ethylene) and is equipped with ports for a calibrated thermocouple,

pH electrode, and addition funnel. The top of the assembly is insu-
lated and the entire cell rests on a magnetic bar stirring plate. A low
power laser beam is passed through the solution and is detected using
a silicon photodiode. The signal is amplified and viewed on an oscil-
loscope.
ADDITION
pH THERMOCOUPLE
INSULATION
To Circulator
LASER DETECTOR DISPLAY
STIR BAR
From
GLASS JACKETED CELL
STIRRING PLATE
FIGURE 7. Block diagram of the solubility apparatus.
The experimental apparatus was tested with KCl, Figure 8. Good

agreement with the literature reports from a number of different labo-
ratories was obtained.22 (For citations of the data given in Figures 8
and 9, the reader is referred to Ref. 22). The error bars associated
with the data from this work arise from repetitive measurement of the
temperature of the SLE point.
DIAL 40395-1 38
7.25
Present Work
Zhang
6.75 Silcock
ESP
Solubility [mol KCl/kgH2O] 6.25
5.75
5.25
4.75
300.0 310.0 320.0 330.0 340.0 350.0 360.0
Temperature K
FIGURE 8.KCl Solubilities determined with the experimental

apparatus and compared to literature data and ESP model results.
3.5
mol Na3PO4/kg H2O
3.0 Apfel
2.5 Kobe
2.0
Wendrow
1.5
ESP
1.0
0.5 Present Work
0.0
270.0 280.0 290.0 300.0 310.0 320.0 330.0 340.0
Temperature [K]
FIGURE 9. Solubilities of Na3PO4.
The method is currently being applied for determination of the

phase behavior of the double salts that have been identified in the
Hanford inventory, Na7F(PO4)2.19H2O, Na3FSO4, and Na6(SO4)2CO3.
Literature results on these system are scarce, however, recent work by
Herting at Numatec Hanford Corporation, and by Weber and by
Beahm et al. at Oak Ridge National Laboratory have been performed
on Na7F(PO4)2.19H2O.30-32 Initial experimental studies on the Na-F-
PO4 system were begun to provide addition data.
Determination of the phase diagram of a double salt requires the

determination of the solubilities of the individual components, i.e.,
NaF, and Na3PO4 and then further observations with mixed solutions.
DIAL 40395-1 39
Results for Na3PO4 are given in Figure 9 where ESP calculations and
the results of previous work have been included. The plot illustrates
some of the typical scatter observed in solubility data from different
laboratories. The experimental results obtained in this work follow
the available experimental data and the ESP calculations except in the
small temperature range between 300 and 310 K where ESP predicts
a gradual increase in solubility followed by a region of near constant
solubility. ESP solid phase results predict that the octahydrate form of
trisodium phosphate (Na3PO4.8H2O) comprises the bulk of the solids
speciation at temperatures greater than 310 K. Another hydrate,
Na3PO4.12H2O, is present at lower temperatures and both crystal
structures may exist in the region of constant and slightly increasing
solubility between 300 and 310 K. Further measurements are in
progress to determine additional solubilities in the transition region
and to examine whether the possible influence of kinetic effects. Fol-
lowing these experiments the solubility for NaF will be obtained and
this will complete the arms of the phase diagram and also provide
additional data for comparison to the literature.
Comparison of ESP predictions with those of the SOLGASMIX Model.

One method of validating the ESP model is to examine its predictive
capabilities for a system of critical interest to the Hanford tank
wastes. One such system is sodium-fluoride-phosphate. Experimental
solubilities have been measured by Herting for natrophosphate as a
function of [OH]-.30 The solubility envelope was then predicted by
Beahm, et al., using the SOLGASMIX model.32 ESP predictions can
be compared to these recent studies.
DIAL 40395-1 40
1.00
E.C. Beahm et al., 3 m OH-

0.90
ESP Prediction, 3 m OH-
0.80 E.C. Beahm et al., 1 m OH
ESP Prediction, 1m OH
Phosphate in Solution, (m)

0.70 E.C. Beahm et al. (in water)
ESP Prediction (in water)
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0.00 0.20 0.40 0.60 0.80 1.00 1.20
Fluoride in Solution, (m)
FIGURE 10. Predicted solubility envelope for Na7F(PO4)2.19H2O.
Figure 10 provides results of the ESP and SOLGASMIX predic-

tions of the solubility envelope for the Na-F-PO4 systems as a func-
tion of [OH].22,32 It is evident that the solubilities predicted by the two
models for the pure components NaF and Na3PO4, differ. In water
ESP predicts, the solubility of NaF as 0.823 m while the SOLGAS-
MIX model estimates 0.974.m. The solubility of Na3PO4 from SOL-
GASMIX was determined to be 0.807 m while a value of 0.929 m
was found using the ESP code. Differences in agreement were also
found at the different hydroxide concentrations investigated and for
the invariant points. For the mixed compositions, the ESP solubilities
are larger than those from the SOLGASMIX model in pure water,
agree well at 0.1 m [OH]-, and are lower than the solubilities from
SOLGASMIX at the 0.3-m [OH]- condition.
These differences are thought to reflect the sources of the funda-

mental thermodynamic data called by the respective codes. The
invariant points, for example, which predict the existence of two solid
phases and a liquid composition, is required information for under-
standing the behavior of the waste in the Hanford tanks. Knowledge
of the solubility envelope for the Na-F-PO4, and other waste constitu-
DIAL 40395-1 41
ents will prevent the fouling of transfer lines and components during
retrieval operations. Incorporation of the fundamental data used in the
SOLGASMIX modeling study within the ESP database will permit
an assessment of the influence of the fundamental data on the code
predictions.
Modeling of saltcakes and comparison to experimental results. As

noted
in the introduction, little is known about the pretreatment require-
ments and compositions of the saltcakes present in the Hanford
inventory. A companion experimental program was begun at
Numatec Hanford Corporation and results of these studies have been
released.33 This work and the data obtained, provide a vehicle for
additional comparison of the ESP model predictions with experimen-
tal data.
The Hanford saltcakes examined were from tanks BY-106, BY-

102, and B-106 and were selected because of the unique character of
the inventory in each. It was anticipated that these tanks would pro-
vide a measure of the application range of the ESP model by virtue of
the widely differing composition in each tank, Table 3.
TABLE 3. Majoranions present in select

Hanford Tanks (in ppm).
BY-106 BY-102 B-106
F- 5,130 18,000 1,540
Cl- 2,060 1,220 1,530
NO2- 32,100 13,900 7,840
NO3- 329,000 95,000 195,000
PO43- 5,270 27,000 75,700
TIC 7,360 27,800 370
SO42- 11,300 57,700 14,800
DIAL 40395-1 42
Herting and Edmundson performed sequential dilution experi-

ments on each saltcake sample. The concentrations of pertinent
anions and cations were obtained and served, along with the tempera-
tures and diluents investigated, as input to the ESP model. At each
dilution Herting and Edmundson determined the specific gravity of
the resulting supernate. The original sample weights and dilution con-
ditions and the concentrations of the ionic species represented the ini-
tial data for comparison to the ESP code.
An abbreviated discussion of the results obtained for the saltcake

from Tank BY-106 is presented below. Full details of these and the
other simulations involving the samples from Hanford tanks BY-102
and B-106 can be found in the report cited previously.22
Comparison of the model predictions and the experimental con-

centration determinations for the nitrate anion (NO3-2) are given in
Figure 11. Quite noticeable in the calculated results is the increase in
nitrate concentration that corresponds to the percent dilution where
the sodium nitrate is predicted to completely dissolve. A similar
result is observed in the experimental data, however, the maximum
concentration is shifted toward slightly higher dilution. Experimen-
tally it appears that all of the sodium nitrate in this saltcake sample
will dissolve between 51% and 100% dilution. Some discrepancy is
also observed with the absolute values of the nitrate anion concentra-
tion. One possible explanation for this disagreement rests on the elec-
troneutrality constraint imposed on the ESP program. To maintain a
balance of positive and negative charges the software will adjust the
concentrations of various anions or cations. For this waste, and much
of the other waste at Hanford, the main anion present is nitrate.
Assuming an excess of sodium ions, but still remaining within exper-
imental error, it is not unlikely that the model will add nitrate to
achieve a net charge of zero.
DIAL 40395-1 43
400
NO3, ESP
350
NO3, D. Herting Data
300
Concentration, g/L 250
200
150
100
50
0
0 100 200 300 400 500
Dilution, Weight Percent
FIGURE 11. Comparison of experimental and predicted results

for nitrate anion concentration – Tank BY-106.
At dilutions greater than 100% (1:1 by weight) the agreement

between the ESP model predictions and the experimental results is
excellent. This behavior was observed to hold for other single salt
anions, such as oxalate (C2O4-2) and chloride. Somewhat more com-
plicated behavior was predicted for the phosphate and sulfate anions.
Figure 12 is a plot of the concentration of the sulfate anion against
percent dilution. At dilutions greater than about 200% the predicted
concentration seems to be within 20% of the experimental result. In
the lower dilution range a considerable difference between the results
is observed. The sulfate may be partitioned in the solid phase between
Na3FSO4 and Na6(SO4)2CO3. Both of these solids were predicted by
the ESP model; however, as discussed in connections with the studies
on the Na-F-PO4 system, some questions remain as to the results pre-
dicted by ESP for double salt systems. Further comparisons of the
ESP data with the saltcake results will involve the determination of
the solid phase constituent at NHC. From these data it will be possi-
ble to evaluate the solids speciation predicted by the code and deter-
mine if additional solids are present which compete for those anions,
sulfate, phosphate and fluoride, that participate in double salt forma-
tion.
DIAL 40395-1 44
SO4, ESP
6
SO4, D. Herting Data
5
Concentration, g/L
4
0
0 100 200 300 400 500
Dilution, Weight Percent
FIGURE 12. Comparison of experimental and simulation

results for sulfate anion – Tank BY-106 (25°C).
Similar results were observed for the saltcakes from tanks BY-
102 and B-106. In most cases, the ESP prediction of anion concentra-
tions from the single salts agrees with the experiments at high dilu-
tion (lower ionic strength). At low dilution values (high ionic
strengths) the code predictions appear to require attention. These
needs are being addressed in the experimental work and in further
comparison of the model to other Hanford streams.
Application of ESP to crust remediation options for Hanford Tank 241-

SY-101. Recent observations of the crust layer in Hanford tank 241-
SY-101 (SY-101) have indicated that the thickness is increasing. The
growth of the crust has been estimated at 2 in. per quarter and the
location of the surface is approximately 14 in. below the single-shell
portion of the tank.34 Workers at Hanford have considered spraying
2M NaOH or inhibited water directly on the crust. In this manner it
was thought that the crust volume, and, perhaps, the combined vol-
ume of the liquid/solid inventory in the tank could be reduced.
Customers at the site requested the use of ESP for modeling the
SY-101 crust problem. Initial efforts concerned the direct addition of
diluent to the tank. These results are summarized below. Others simu-
DIAL 40395-1 45
lations involving the transfer of 100,000 gallons of SY-101 liquid to a

receiving tank (241-SY-102) were also considered. The results from
both of the studies have previously been distributed as letter reports
and are also contained in the report to the focus area.22-24
Data for the simulation were taken from the TWRS Best Basis
Inventory for SY-101.35 The total weight of the various anions, cat-
ions and radionuclides were used with the reported total volume of
liquid and solid inventory to estimate concentrations of the tank con-
stituents. The temperatures of the tank are monitored, near the tank
risers, using thermocouples.35 Averaging of these results yielded a
temperature of 45˚C. The concentration data were reconciled for elec-
troneutrality and the pH of the tank was calculated. These operations
and conversion of the input ionic concentrations to a composite
molecular stream was performed using the ESP Water Analyzer tool.
A characterization of core samples from SY-101 was previously

reported by Person.36 Initial comparison of the simulation results with
the experimental solids distribution revealed poor agreement in the
distribution of the organic carbon components. Thus, the ESP model
was tuned by varying the ratio of oxalate to acetate. The resulting dis-
tribution along with that obtained by Person is collected in Table 4.

in simulation with core sample analysis of Person.36
ESP Prediction Person3

Species Weight % Weight %
Cr(OH)3 4.1 5±1
NaNO3 35.0 21 ± 7
Ni(OH)2 0.2 NR
UO2(OH)2 ca. 10-1 NR
Ca(OH)2 0.4 NR
Na6(SO4)2CO3 3.4
DIAL 40395-1 46

in simulation with core sample analysis of Person.36
ESP Prediction Person3

Species Weight % Weight %
Na2C2O4 12.1 12 ± 4
Na2CO3 1H2O 35.5 31 ± 7
NaCl 0.1 NR
Na7F(PO4)2.19H2O 4.1
NaNO2 5.2 12 ± 3
Al(OH)3 Not observed 4±5
Na3PO4 4±3
Na2SO4 4±2
Good agreement is observed for chromium hydroxide, sodium

carbonate, and sodium oxalate. The sodium nitrate weight fraction is
larger than that reported by Person and the percentage of sodium
nitrite predicted by ESP is from ca. 4% to 9% lower than that of the
core sample. Using the upper limit error estimates from the labora-
tory data, the total sodium nitrate and sodium nitrite percentage
would be 43%. This value is slightly higher than the corresponding
total (40%) from the simulation. Fair agreement was also observed in
comparing the double salt weight fractions and those of the base sin-
gle salts reported by Person. For example, the fraction of sodium sul-
fate from the core sample (4 ± 2%) is consistent with the ESP
prediction for the associated Na6(SO4)2CO3 double salt (3.4%).
Adding either 2M caustic or inhibited water using an ESP Process

Mix block simulated in situ dissolution of the SY-101 crust. The ESP
model describes equilibrium chemistry. Simulation of the fate of any
trapped gases, such as the hydrogen associated with the SY-101 crust,
is outside of the basic thermodynamic framework. Within the code, it
is possible to entrain solids in liquid or vapors in liquid; however, as
soon as an equilibrium condition is achieved, the gas will be parti-
DIAL 40395-1 47
tioned according to the specific solubility. Hydrogen has limited solu-

bility in water at a pH of 15.2 and an accurate measure of the volume
of hydrogen liberated, which will effect the total waste volume in the
tank, relies on an assumption that the gas will be liberated at a rate
consistent with solids dissolution.
TABLE 5. Solid phase species distribution - 2M NaOH addition.
% of 2M NaOH Added (By Weight)
0 1 2 3 4 5
Species*
Cr(OH)3 4.07e+04 4.06e+04 4.06e+04 4.07e+04 4.07e+04 4.07e+04
NaNO3 3.46e+05 3.17e+05 2.81e+05 2.42e+05 2.03e+05 1.63e+05
Ni(OH)2 1.49e+03 1.49e+03 1.49e+03 1.49e+03 1.49e+03 1.49e+03
UO2(OH)2 5.32e+01 2.61e+01
Ca(OH)2 4.18e+03 4.18e+03 4.18e+03 4.19e+03 4.18e+03 4.18e+03
Na6(SO4)2CO3 3.38e+04 3.30e+04 3.20e+04 3.09e+04 2.97e+03 2.85e+04
Na2C2O4 1.20e+05 1.20e+05 1.20e+05 1.20e+05 1.20e+05 1.20e+05
Na2CO3 1H2O 3.52e+05 3.46e+05 3.39e+05 3.33e+05 3.25e+05 3.17e+05
NaCl 6.41e+02
Na7F(PO4)2.19H2O 4.04e+04 3.74e+04 3.68e+04 3.68e+04 3.67e+04 3.64e+04
NaNO2 5.11e+04 1.01e+04
Total Solids (kg) 9.9e+05 9.1e+05 8.55e+05 8.09e+05 7.34e+05 7.11e+05
Tables 5 and 6 provide the results of the simulations for in situ

dissolution of the tank contents using 2M NaOH. Similar results were
obtained for the addition of inhibited water and can be found in the
original reference.23 The chromium, nickel, and calcium hydroxides
were predicted to be insoluble at the pH and ionic strengths encoun-
tered. Weights for sodium oxalate and the sodium-fluoride-phosphate
double salt were not predicted to change significantly over the range
of dilutions studied. Major changes in the total mass of the solid
DIAL 40395-1 48
phase arise from dissolution of the sodium nitrate and sodium carbon-
ate.
TABLE 6. Additional simulation results for the 2M NaOH addition
% 2 M NaOH Added (by Weight)
0 1 2 3 4 5
Solids
Total Mass (kg) 9.90e+05 9.09e+05 8.55e+05 8.09e+05 7.60e+05 7.11e+05
% Change 0.00 -8.14 -13.66 -18.30 -23.24 -28.18
Total Volume (l) 4.32e+05 3.95e+05 3.71e+05 3.51e+05 3.19e+05 3.07e+05
% Change 0 -8.47 -14.12 -18.82 -26.23 -28.82
Density (g/l) 2292 2301 2304 2307 2385 2313
Supernate
Total Mass (kg) 5.80e+06 5.96e+06 6.08e+06 6.19e+06 6.31e+06 6.43e+06
% Change 0.00 2.59 4.70 6.68 8.68 10.69
Total Volume (l) 3.97e+06 4.08e+06 4.16e+06 4.25e+06 4.33e+06 4.41e+06
% Change 0.00 2.59 4.78 6.87 8.98 11.08
Density (g/l) 1461 1461 1460 1458 1457 1456
Ionic Strength 21.81 21.74 21.52 21.27 21.03 20.81
pH 15.19 15.18 15.16 15.14 15.12 15.10
Process Information
%Solids by Weight 14.58 13.23 12.33 11.56 10.75 9.96
Total Mass in Tank 6.79e+06 6.86e+06 6.93e+06 7.00e+06 7.07e+06 7.14e+06
Total Volume in Tank 4.41e+06 4.47e+06 4.53e+06 4.60e+06 4.65e+06 4.72e+06
Volume Inc % 0.00 1.50 2.93 4.35 5.52 7.17
Figure 13 compares the total solids weight for the two diluents. It
is evident that the use of inhibited water results in a slightly larger
dissolution of solids. This is expected, as the salts, which are dissolv-
ing, are sodium salts; thus, the introduction of sodium into the system
via the use of 2M NaOH will suppress the dissolution of the nitrate
and carbonate containing salts.
DIAL 40395-1 49
1.1E+06
1.0E+06
2M NaOH
9.5E+05 Inhibited Water

Total Solids Weight (kg)
9.0E+05
8.5E+05
8.0E+05
7.5E+05
7.0E+05
6.5E+05
6.0E+05
0 1 2 3 4 5 6
% Dilution by Weight
FIGURE 13. Predicted solids mass in SY-101 during in situ dilution.
It has been estimated that 10% of the volume within SY-101 is

composed of H2.37 All of the hydrogen must be in direct physical con-
tact with the solid phase else it would be free to evolve from the tank.
At 10% of the total tank volume the hydrogen would occupy 4.41 x
105 L. At an addition of 4% by weight of inhibited water, the ESP
model predicts 7.10 x 105 kg of solids remaining in the tank. This
amounts to a dissolution of roughly 2.8 x 105 kg of the original solid
phase. By assuming a direct proportionality of H2 evolution to total
solids mass, the amount of gas released upon addition of 4% by
weight of inhibited water would be 1.29 x 105 L. Subtracting this
value from the final tank volume predicted following the 4% (by
weight) addition of inhibited water, yields a contents volume of 4.48
x 106 L. This value is larger than the current volume of 4.41 x 106 L
and, consequently, other options for reducing the crust may be more
appropriate.
DIAL 40395-1 50
The additional studies on options for remediation of the SY-101

crust are contained in Ref. 24. These calculations describe the effects
of solids entrainment; the diluent needed to prevent solids formation
in the transfer line between SY-101 and the receiving tank, tempera-
ture effects, and the results of mixing the SY-101 transfer stream with
the receiving tank contents. Further simulations on SY-101 are in
progress to determine possible reasons for the recent waste changes
and observed crust growth.
Conclusions
Considerable progress has been made in modeling the dissolution

of saltcakes from three different Hanford tanks, and in evaluating var-
ious aspects of the ESP code. Model characterization efforts have
been started by:
•examining the fundamental thermodynamic constants inher-
ent to the compilations used in the software that are spe-
cifically applicable to the Hanford inventory;
•performing experiments to obtain solubilities in systems
which represent knowledge gaps in the data;
•running and interpreting simulations on waste saltcakes that
are being characterized at the site; and
•modeling tank contents and remediation efforts.
In examining the fundamental data it was noted that excellent

agreement between the Gibbs free energy of formation and the
enthalpy of formation was observed in comparing the data contained
in the ESP databases and the critically evaluated NIST and CODATA
compilations. For most systems evaluated, except for simple salts
containing fluoride ion, the agreement with the standard state entropy
values was reasonable. Data for the heat capacity are limited and scat-
tered across all data sources.
DIAL 40395-1 51
An experimental apparatus was developed and tested for determi-

nation of system solubilities. Studies on the Na-F-PO4 system were
initiated with measurements on Na3PO4. The experimental results for
this system were observed to be in good agreement with other litera-
ture data and with ESP model predictions. Some solubility discrepan-
cies were noted in a composition/temperature regime where multiple
crystal forms are expected.
A comparison of the predictions of the ESP model with a second

thermodynamic code (SOLGASMIX, ORNL) was performed for the
Na-F-PO4 system. Differences in the phase behavior observed from
the two models are thought to reflect the fundamental data used.
Additional comparisons with the two codes are planned for other
double salt systems and through further examination of the data.
An extensive modeling effort was initiated on saltcake dissolu-

tion. The simulations correctly predicted the composition of the
supernate phase, compared to the experimental results, at dilutions
greater than 1:1. At lower dilution ratios, the code tended to underpre-
dict the ions associated with double salts. One factor, which has been
implicated in this work, is the lack of substantial information on the
double salts.
Finally, from a direct customer request, the ESP code was used to
model remediation options for the crust layer in Hanford tank 241-
SY-101. Results presented here indicate good agreement between the
code predictions and a previous core sample analysis. The original
solids loading in the tank was calculated as 14.6%. Upon addition of
4% by weight of inhibited water, the solids loading is reduced to 11%
by weight. The addition resulted in a total volume increase, assuming
the trapped hydrogen in the crust would evolve in direct proportion to
solids dissolution, compared to the original waste content level. Work
on evaluating the effects of transferring a portion of the waste to a
receiving tank have been reported elsewhere (Ref. 24) and additional
simulations on SY-101 are continuing.
DIAL 40395-1 52
Project Status
Work on evaluation of saltcakes using ESP and on code validation

is continuing. The Tank Focus Area has also asked us to participate in
a study on feed stabilization, which is expected to begin in January.
Work Planned
Improved confidence in the predictive capabilities of the code

relies on the quality of the fundamental data and on comparison of the
results from the model to actual experimental data. The developed
solubility apparatus will be used to continue the phase diagram work
on the Na-F-PO4, Na-F-SO4, and Na-SO4-CO3 systems. Further eval-
uation of the ESP and SOLGASMIX models will be undertaken by
examining the
Na-F-SO4, and Na-SO4-CO3. Evaluating the variance in predic-

tions at different error levels for selected input streams will assess
model sensitivities.
Continued experimental studies of Hanford saltcakes will be con-

ducted at Numatec Hanford Corporation. The existing comparison is
limited to the supernate phase and knowledge of the composition of
the solid phase distribution will pinpoint those specific molecules that
are effecting the ESP results.
Some additional simulations designed to evaluate the processes

that have occurred in Hanford tank 241-SY-101 are planned. A sec-
ond Phase I feed tank will also be modeled.
References
18. MacLean, G. T., “Computer Simulation of Laboratory Leaching and

Washing of Tank Waste Sludges,” WHC-SD-WM-E5-312, Westinghouse
Hanford Company, Richland, Washington, October 1994.
DIAL 40395-1 53
19. Reynolds, D. A., “Practical Modeling of Aluminum Species in High-pH

Waste,” WHC-EP-0872, Westinghouse Hanford Company, Richland,
Washington, 1995.
20. Kirkbride, R. A., ”Tank Waste Remediation System Operation and Utiliza-
tion Plan,” HNF-SD-SP-012, Rev. 0, Numatec Hanford Corporation, Rich-
land Washington, September 1997.
21. “Data Presented at the Saltcake Dissolution Workshop,” DIAL, Missis-

sippi State, MS, May 1998.
22. Modeling, FY 1998 Status Report,” DIAL 40395-TR98-3, Diagnostic

Instrumentation and Analysis Laboratory, Mississippi State University,
October 1998.
23. Lindner, J. S. and Toghiani, R. K., “Thermodynamic Simulation of Tank

241-SY-101 Dissolution-Part 1: in situ Crust Dissolution”, DIAL 40395-
TR98-1, Diagnostic Instrumentation and Analysis laboratory, Mississippi
State University, August 1998.
24. 241-SY-101 Dissolution-Part 2: Supernate Transfer Followed by In-Tank

Dilution,” DIAL 40395-TR98-2, Diagnostic Instrumentation and Analysis
laboratory, Mississippi State University, October 1998.
25. The NBS Tables of Chemical Thermodynamic Properties, J. Phys. Chem.

Ref. Data.
26. Supplement 2, (1982). Cox, J.D., and Wagman, D.D., CODATA KEY Val-
ues for Thermodynamics, Hemisphere, New York (1989).
27. Nuclear Energy Agency website www.nea.fr/ml/science/chemistry/

www.tbd database.
28. Wyatt, D. K. and Grady, L. T., “Determination of Solubility, Physical

Methods of Chemistry, Vol. VI,” in Determination of Thermodynamic
Properties, 2nd ed., Rossiter, B. W. and Baetzold, R.C., Eds. Wiley, New
York, 1996.
29. Zhang, L. et al.,” Measurement of Solid-Liquid Equilibria by a Flow-

Cloud-Point Method,” J. Chem. Eng. Data, 43, 32 (1998).
DIAL 40395-1 54
30. Herting, D.L., “Clean Salt Process Final Report, Appendix A, WHC-EP-
0915, Numatec Hanford Corporation, Richland, Washington, 1996.
31. Weber, C. F., “A Solubility Model for Aqueous Solutions Containing

Sodium, Fluoride, and Phosphate,” Ph.D. Dissertation, The University of
Tennessee, Knoxville, May 1998.
32. Beahm, E. C., et al.,”Status Report on Solid Control in Leachates,” ORNL/

TM-13660, Oak Ridge National Laboratory, Oak Ridge, Tennessee, 1998.
33. Herting, D. L. and Edmundson, D. W., “Saltcake Dissolution FY 1998 Sta-

tus Report,” HNF-3437, Rev. 0, Numatec Hanford Corporation, Richland,
Washington, 1998.
34. Blain Barton, personal communication (July 3,1998)
35. Twins II website, http://twins.pnl.gov:8001/htbin/TCD/getTableList.exe
36. Person, J.C., “Effects of NaOH Dilution on Solution Concentrations in

Tank 241-SY-101 Waste”, WHC-SD-WM-DTR-045, Rev. 0, December
1996.
37. Meyer, P.A., et al., “Gas Retention and Release Behavior in Hanford Dou-
ble-Shell Waste Tanks”, PNNL-11536, Rev. 1, May 1997.
DIAL 40395-1 55
TASK 4 Product Acceptance Support
Subtask 4.1. Monitors for Idaho LAW Stream

D. L. Monts, C. B. Winstead, G. P. Miller
Introduction
Purpose
Currently, Idaho is developing a design of a facility to immobilize

HLW from the Idaho Chemical Processing Plant. Most of the HLW is
in the form of a dry calcine, stored in bins. The present design calls
for dissolution of the calcine, and separation of the fission products
and actinides from the inert chemicals contained in the calcine. The
resulting stream containing the inert chemicals will be immobilized
by grouting, and then disposed of as low-level waste.
This strategy is predicated on the success of the separations pro-

cess. Currently, no method is available to directly determine the con-
tent of the TRU and other important elements in this product stream.
As a result, a number of “surge” tanks have been included in the pro-
cess to allow the product stream to be sampled, and then analyzed
off-line elsewhere. Based on these analyses, a decision will be made
of whether the low activity fraction of the dissolved HLW (LAW) can
DIAL 40395-1 56
Task 4. Product Acceptance Support
be treated as low level waste. This determination will depend on the

concentration of actinides in the LAW.
DIAL will adapt an existing laser-based system so that it can be

used to make this determination on-line in near real-time. This will
greatly reduce the cost of the facility (by eliminating surge tanks),
and improve the process cycle time. It will also help avoid the risk
associated with handling these samples in highly radioactive facili-
ties.
DIAL currently has two laser-based techniques with the ability to

distinguish isotopic species: high resolution laser-induced fluores-
cence (HR-LIF), and cavity ringdown spectroscopy (CRDS). The first
year’s activities will concentrate on determining the detection limits
of each technique for the isotopes of interest to INEEL. Based on the
demonstrated detection limits of each instrument, a selection of the
instrument concept to be utilized will be made. Subsequent efforts
will concentrate on optimizing the instrument for field deployment.
Based on the optimization, a prototype instrument will be used for a
radioactive demonstration. This, in turn, will be the basis for s specifi-
cation for a monitoring system.
Methodology
Two different techniques to address this need are being investi-

gated: cavity ringdown spectroscopy and laser-induced fluorescence
spectrometry.
Cavity Ringdown Spectroscopy. Cavityringdown spectroscopy

(CRDS) is a relatively new variant of absorption spectroscopy that
has demonstrated extreme sensitivity in a variety of studies.38 The
ringdown technique (Fig. 14) has been described in a number of pub-
lications, and will only be briefly summarized here. In “traditional”
cavity ringdown spectroscopy, a laser pulse from a tunable pulsed
laser is introduced through the end mirror of a stable optical cavity.
DIAL 40395-1 57
This optical cavity is formed from two highly reflective mirrors, and
serves to trap the fraction of the laser pulse that enters the cavity. The
laser pulse propagates back and forth between the mirrors, where it
can interact with an absorbing medium in the cavity over the course
of thousands of round trips inside the cavity. Since the mirrors are not
perfectly reflective, some of the laser light is transmitted through the
mirrors each time the light is reflected. A photomultiplier tube is
placed behind the second mirror to detect the intensity of laser light
transmitted through the mirror as a function of time. The time for the
pulse energy in the cavity to decay is determined by the reflectivity of
the mirrors and by the absorption of the sample in the cavity. When
the cavity is empty, the decay time yields a measurement of the cavity
mirror reflectivities. As the absorption in the cavity increases, the
decay time for the light in the cavity decreases. By inserting into the
cavity an appropriate atomization source, such as an inductively cou-
pled plasma (ICP) or graphite furnace, various chemical forms of
TRU elements can be atomized and detected using CRDS.
FIGURE 14. Schematic of cavity-ringdown spectroscopy technique.
DIAL 40395-1 58
Laser-Induced Fluorescence Spectrometry. Laser-induced fluores-

cence (LIF) spectrometry is a well-established, robust technique for
detecting species of interest at low concentrations. In the LIF tech-
nique (Fig. 15), an electronic state of the species of interest is excited
with a tunable laser and the resulting fluorescence intensity is moni-
tored as a function of laser wavelength. Since the mass of isotopes are
different from one another, the corresponding atomic energy levels
are slightly different (Fig. 16). Consequently, when a sufficiently
high-resolution tunable laser is scanned across an atomic electronic
transition, the resulting LIF spectrum contains a peak associated with
each isotope present; the intensities of the isotopic peaks are directly
related to the concentration of the isotopes. Hence the isotopic abun-
dances can readily be obtained from the LIF spectrum. In order that
the individual isotopic transitions can be resolved, it is necessary that
the species of interest be in the gas-phase. For the TRU elements of
interest, an atomization source is required in order to volatilize and
atomize the sample. A calibration curve is obtained by recording the
LIF signal intensity as a function of concentration. Using the calibra-
tion curve, unknown concentrations can be determined.
Narrowband Atomization
Laser Source
Lens
Spectrometer
Detector
FIGURE 15.Schematic of the laser-induced fluorescence
spectrometry technique.
DIAL 40395-1 59
U-238
Isotope shift
U-235
U-238 Emission
Intensity
U-235
U-235 U-238
Wavelength λ
FIGURE 16. Schematic of isotopic energy shifts and the associated LIF
spectrum.
Work Accomplished
Cavity Ringdown Spectroscopy
The most critical elements necessary for assembling an ultrasen-

sitive CRDS system are high-quality cavity mirrors. Typically to
achieve extreme sensitivity, mirrors of greater than 99.9% reflectivity
are required. However, atomic spectrometry requires the use of ultra-
violet laser light, a region of the spectrum where mirror reflectivity is
often relatively poor. Thus, the first challenge to be overcome for cav-
ity ringdown in elemental spectrometry is obtaining high-reflectivity
mirrors for ultraviolet wavelengths. While standard optical suppliers
will only guarantee 99.5% reflectivity for ultraviolet wavelengths, a
thorough search resulted in finding one company willing to quote
99.9% reflectivity mirrors for ultraviolet use. Figure 17 depicts a ring-
down signal obtained using mirrors coated by this company for maxi-
mum reflectivity around 360 nm. (Uranium has a strong absorption at
358.4 nm). These mirrors have a 6-meter radius of curvature and were
separated by 57 cm of air when this waveform was recorded. The
depicted waveform has a decay time of 5 microseconds. After cor-
recting for the amount of loss due to scatter from the air in the cavity,
the reflectivity of the mirrors can be determined from this ringdown
DIAL 40395-1 60
time and is ~99.965%. Thus contrary to statements in the literature,

excellent mirrors are available for cavity ringdown at ultraviolet
wavelengths. Mirrors with 99.9% reflectivity have also been obtained
for 280 nm operation.
358 nm Mirrors
Relative Intensity
-5E-06 0 5E-06 1E-05 2E-05 2E-05

Seconds
FIGURE 17.Cavity ringdown decay for air with mirrors optimized
for 360-nm operation.
The original plans for this project included measurements of ura-

nium standards using cavity ringdown in both inductively coupled
plasma and graphite furnace systems. However due to regulatory
requirements, the use of uranium is not permitted at this time. Instead
we have used chromium as a surrogate in the ICP for measurements
at almost precisely the same wavelength as would be used for ura-
nium, demonstrating the feasibility of using this spectral region for
ICP ringdown measurements. Figure 18 depicts a cavity ringdown
spectrum of the chromium absorption at 357.9 nm, obtained when a
1-ppm chromium standard solution was injected into the ICP. Due to
difficulties beyond our control encountered upon installation of a new
narrow linewidth laser system, this data was obtained with a laser lin-
ewidth that is broader than the absorption line. As with traditional
DIAL 40395-1 61
absorption spectroscopy, using a broad linewidth source leads to a

reduction in measurement sensitivity since only a fraction of the light
is resonant with the strongest part of the atomic absorption. The new
narrow linewidth laser system has now been successfully installed,
allowing for detection limit determination in the near future.
Ringdown Time
(1 ppm Chromium)
1.4
1.2
Microseconds
0.8
0.6
0.4
3578 3578.5 3579 3579.5
Wavelength (Å)
FIGURE 18. Cavity ringdown spectrum of atomic chromium

absorption at 357.9 nm.
We also have recently collected some preliminary data that dem-

onstrates the utility of cavity ringdown for elemental spectrometry in
graphite furnace sources. Using mirrors coated for 280-nm operation
with 99.9% reflectivity, changes in ringdown time have been mea-
sured that are associated with the atomization of lead standard solu-
tions. This preliminary data, which was acquired using a somewhat
crude manual timing scheme for acquiring data (essentially a stop-
watch), seems to indicate results comparable to commercial atomic
absorption systems. This is very encouraging when considering that
we have not yet optimized many experimental parameters (such as
data acquisition timing and speed) and that the broad linewidth laser
source was also used. The total atomization time in a graphite furnace
DIAL 40395-1 62
is typically on the order of one second, so the fact that usable data is
obtained with manual timing is a testament to the sensitivity of the
ringdown method, as we almost assuredly were not measuring during
the optimum atomization time. We are currently improving our acqui-
sition system and are working toward a more quantitative analysis of
this data.
Finally, this work and other related atomic cavity ringdown

efforts have been presented at the U.S. Department of Energy's Envi-
ronmental Management Science Program (EMSP) workshop in Chi-
cago and abstracts have been submitted to the Federation of
Analytical Chemistry and Spectroscopy Societies Conference, the
Gaseous Electronics Conference, and the Southeastern Section of the
American Physical Society Conference.
Laser-Induced Fluorescence Spectrometry
During this reporting period, we concentrated on efforts to record

and deconvolute the isotopic spectrum of a surrogate, copper, in order
to demonstrate the deconvolution technique. Copper was selected
because it has only two naturally occurring isotopes, both isotopes
are present in significant abundance, and the separation of the isoto-
pic transitions (although smaller than for uranium) should have been
almost resolvable with our current dye laser system. In order to maxi-
mize the intensity, initial experiments were performed with high con-
centrations of copper. Deconvolution analysis of these spectra
indicated that in addition to atomic transitions, molecular transitions
also occurred in the spectra region, inhibiting resolution of the isoto-
pic transitions. These experiments were repeated using lower concen-
trations. The resulting LIF spectra could not be resolved even using
deconvolution because the linewidth of our tunable dye laser was
broader than the isotopic separation for this copper transition. The
linewidth of the dye laser was narrowed by inserting an etalon into
the dye laser's oscillator cavity; however, it was discovered that the
wavelength of the dye laser can no longer be scanned under computer
DIAL 40395-1 63
control. We are currently modifying our dye laser so that the narrow-
linewidth dye laser can be pressure scanned. This is done by pressur-
izing the dye laser oscillator cavity with an inert gas, such as nitro-
gen, to a pressure of up to 30 psig and then allowing the gas to
escape. Since the index of refraction of the gas in the oscillator cavity
is a function of pressure, changing the pressure in the oscillator cavity
changes the lasing wavelength. The technique is simple, but it has
three disadvantages: (1) since the rate at which the gas escapes the
cavity is non-linear, the scan rate of the laser wavelength is also non-
linear; (2) since the operational conditions (exact initial pressure and
how valve is opened) are slightly different from experiment to experi-
ment, the scan rate differs from experiment to experiment; and (3) the
wavelength range over which the dye laser can be pressure scanned in
a single experiment is limited. The use of a pressure-scanned, narrow-
linewidth dye laser will permit us to develop the methodology to han-
dle isotopic LIF spectra, but will not be satisfactory for routine analy-
sis. To the extent possible, we are attempting to perform these
experiments using currently available equipment; what we are too
frequently encountering in the laboratory is proof that the existing
equipment is not adequate for these efforts.
TRU elements are most commonly found in the oxide form. Lab-
oratory flames are known not to efficiently atomize actinide oxides.
Inductively coupled plasmas are more than sufficiently hot enough to
atomize refractory oxides such as those of the actinides. The air ICP
elemental analysis group at DIAL loaned us one of their ICP plasma
systems. After the ICP system had been installed in our laboratory
and preliminary experiments using surrogates had been performed to
optimize operation, we learned that the university did not yet have a
regulatory license to perform experiments with actinides and thus we
were unable to record the LIF spectrum of uranium in an ICP.
DIAL 40395-1 64
Work Planned
Cavity Ringdown Spectroscopy
The primary elements to demonstrate measurement of TRU ele-

ments using cavity ringdown have now been assembled. Very high
quality mirrors have been located and obtained, and demonstration
measurements have been performed in the ICP very near the uranium
absorption wavelength. Graphite furnace cavity ringdown has been
demonstrated as well. A new narrow-linewidth laser system is finally
on-line and operational, and will allow the quantitative demonstration
of ringdown detection limits for species such as uranium. Continuing
progress into the sensitive measurements of TRU elements will be
largely dependent upon MSU and DIAL securing the appropriate
licenses to use uranium in these studies. It is anticipated that in the
coming year, these detection limit measurements will be finalized.
Test measurements of a surrogate for the low activity fraction of the
INEEL high-level waste will also be investigated.
Laser-Induced Fluorescence Spectrometry
In order to make progress on the use of LIF for isotopic determi-

nation of TRU elements, there are three prerequisite needs that must
be meet. The first is that the university must have a regulatory license
to work with actinides The university is currently negotiating with the
state regulatory agency and is purchasing the required monitoring
equipment. It is currently anticipated that the university will have the
appropriate regulatory license by March, 1999. Thereafter we will be
able to work with uranium rather than with surrogates. The second
need is the need for a sufficiently hot atomization source. Funds have
recently been approved for an ICP atomization source; request for
written bids have been distributed by the university's purchasing
office and will be opened in early January, 1999; delivery of the ICP
system is expected before the end of March, 1999. An ICP system
capable of operating with air as the carrier gas is being purchased
DIAL 40395-1 65
since many of the applications for which the LIF technique is applica-
ble involve air. The third need is for a sufficiently narrow-linewidth,
tunable laser system that can be reproducibly scanned. DIAL's cavity
ringdown spectroscopy group will permit us to use their new moder-
ately high-resolution dye laser system to perform some preliminary
experiments on surrogates in an ICP plasma. If as expected these LIF
experiments prove that such a moderately high-resolution tunable
laser system has sufficient resolution for the TRU elements, then a
comparable dye laser system will be purchased during spring, 1999;
if the experiments indicate that even higher resolution is required,
then additional funding will be sought in order to purchase an ultra-
high resolution tunable laser system. In the interim our efforts to pres-
sure scan our current dye laser will continue. A high-resolution dye
laser with computer-controlled scanning mechanism will overcome
all these limitations.
Nomenclature
CRDS cavity ringdown spectroscopy
DIAL Diagnostic Instrumentation and Analysis Laboratory
HLW high-level waste
ICP inductively coupled plasma
LAW low activity waste
LIF laser-induced fluorescence
MSU Mississippi State University
nm nanometer
ppm parts-per-million
DIAL 40395-1 66
TRU transuranic
References
38. See, for example: G. P. Miller and C. B. Winstead. 1997. Journal of Ana-
lytical Atomic Spectrometry. 12:907; and J. J. Scherer, J. B. Paul, A.
O’Keefe and R. J. Saykally. 1997. Chemical Reviews. 97:25.
Subtask 4.2. Pressure in Drums

R. Daniel Costley and Mark Henderson
Introduction
At most waste sites, transuranic (TRU), low-level (LLW), and

mixed low-level (MLLW) wastes are stored in 55 gallon drums. Most
of these drums contain organic materials as well. Radiolysis of the
organic contents of the drums, or other physical or chemical decom-
position mechanisms, may result in pressurization of the drums. In
and of itself this pressurization can represent a serious safety hazard
to the operator who has to open them. In some cases, however, the
pressure may reflect flammable or explosive conditions inside the
drum (e.g., from hydrogen generation), greatly increasing the hazard.
Current DOE practice require opening and inspecting individual

drums. In cases where pressurization has occurred, this practice is a
danger to the worker. Personnel at DIAL have developed a simple
non-intrusive technique that will detect pressures above ambient, and
have demonstrated a first generation prototype at the Paducah and
Oak Ridge sites. Based on feedback from users, a commercial-grade
instrument is desired. This task will produce a commercial-grade
instrument which can be used to provide both a warning of overpres-
surization, and a quantitative assessment of the pressure inside the
DIAL 40395-1 67
drum. The general plan is to use the users’ feedback to upgrade the
prototype, field test the unit, re-engineer the unit based on field test-
ing, and then do proof testing of the re-engineered unit. After comple-
tion of this testing, the feasibility of extending this to larger packages
will be investigated. Negotiations are already underway which should
lead to commercialization of the technology.
Representatives from the Paducah, Oak Ridge, and Savannah

River Sites will assist in developing test plans for the current proto-
type, participate in field testing, and thus assist in refining the concept
and expanding it to other types of containers.
The objective of this task is to develop a commercial monitor for

determining pressure inside closed drums.
Work Accomplished
In order to investigate the effect of drum pressurization on the lid

vibration, several drums were configured so that they could be pres-
surized and so that this pressure could be measured. In order to do
this, two fittings were inserted into the side of a drum near the top. A
valve stem was put into one of these fittings. A pressure gauge was
screwed into the other fitting. This arrangement allowed the drum to
be pressurized and the pressure to be measured independently of the
technique being developed. The vibration of the drum lid was
detected by two means. An accelerometer, which was attached to the
center of the lid with a magnetic coupler, detected the vibration of the
lid directly. A microphone, which was mounted approximately 1 foot
above the lid, detected the sound produced when the lid was tapped.
Therefore, the microphone indirectly detected the vibration of the lid.
An impact hammer with a soft tip was used to strike the lid and cause
it to vibrate. The impulse from the impact hammer was used to trigger
an oscilloscope. The data was then transferred from the oscilloscope
to a microcomputer where it was processed and analyzed. The lowest
mode of vibration of the drum lid was detected with the microphone
DIAL 40395-1 68
since this mode radiates acoustically. Several other modes of vibra-

tion were detected with the accelerometer. The digitized signals were
converted to frequency spectrums via a Fast Fourier Transform which
allowed the frequencies of the different modes to be identified. The
frequency of the lowest mode was correlated to the drum pressure for
several different drum types. These drum types included drums lids
with and without stiffening rings. The drums were also filled with
water at varying levels, up to 80% full. These results show that the fill
level did not influence the frequency response of the drum lid. The
drum and drum lid were modeled using Finite Element Analysis. This
allowed us to investigate the effects of drum thickness and other fac-
tors on the vibration response. There was good agreement between
the FEA results and experiment. It was determined that the frequency
response of the drum increased as the pressure within the drum
increased. The frequency increased approximately 10 Hz/psi for
drum lids with a stiffening ring and 20 Hz/psi for lids without stiffen-
ing ring. FEA showed that the frequency response increased as the
thickness of the drum increased. However, both experimental and
FEA showed that this change was small compared to the change
caused by the stiffening ring.
Conclusions
It has been demonstrated that the frequency of vibration of the lid

on a 55 gallon drum is proportional to the pressure inside the drum.
This dependence of frequency on pressure is being used to develop an
instrument that will detect pressurization within drums. It was shown,
however, that different type drums may require different calibrations,
i.e. those with and without stiffening rings. The ultimate goal of this
work is to design an instrument that can test drums for pressure in the
field. A prototype has already been built. This instrument would ide-
ally be hand held, utilizing a microphone which has certain advan-
tages over an accelerometer. By using a microphone an inspector
would save time since contact with the drum would be minimized.
The inspector would simply tap the drum, the signal would be
DIAL 40395-1 69
recorded with a microphone that was either internal to the device or

attached to a lapel, the signal would be recorded, and the inspector
would move on to the next drum. Another advantage is that the spec-
trum from the microphone signal is usually much simpler, since many
of the higher modes do not radiate acoustically. Thus, the spectrum is
easier to interpret with software.
Work Planned
We plan to investigate the repeatability of the technique by taking

data on many different drum lids. The effects of corrosion on the
drum lid will also be investigated. A field test/demonstration is being
planned at a DOE facility.
Reference
39. Patel, H., Costley, R.D., Henderson, M., Jones, E.W., and Tomlinson, A.
1999. Drum pressure monitor. To be published in Review of Progress in
Quantitative Nondestructive Evaluation, Vol. 18, ed. by D.O. Thompson
and D.E. Chimenti, New York: Plenum Press.
DIAL 40395-1 70
TASK 5 Advanced Cleanup Support:
Robust Immobilization Devices
Subtask 5.1. Hybrid Plasma Induction Cold

Crucible Melter
Dana Miles
Introduction
Russian engineers have developed several melters which are more

robust than current generation furnaces, and which can produce a
wide variety of waste forms ranging from borosilicate glass to crys-
talline ceramics (Synroc). This technology potentially could be used
for the orphaned spent fuel at SRS, Idaho, and Hanford. DOE has
identified disposition of these materials as an “Unmet Need.” This
technology appears to be a way to address this need in an expeditious
manner, while also providing the capability to produce a second gen-
eration waste form in existing facilities.
As part of the Cooperative Agreement, a “hybrid” Russian melter

will be installed and tested at DIAL to determine its usefulness and
limitations. It is similar to the new “next generation” melter, a cold
crucible design with inductive heating. This requires certain compo-
nents in the glass to allow current to flow, and thus effectively heat up
the glass pool. The “hybrid” melter combines the cold crucible design
DIAL 40395-1 71
Task 5. Advanced Cleanup Support: Robust Immobilization Devices
with a plasma torch to initially break down waste components fed to

the melter, negating the need for current inducing components in the
glass feed.
Discussions continue for obtaining the next generation melter and

testing it at DIAL. Future work calls for providing an appropriate
control system for each system. After installation at DIAL, each
melter will be tested with simulated spent nuclear fuel to determine
the feasibility of producing a vitrified product (borosilicate glass) and
a crystalline product (Synroc). Processing and product properties of
the waste forms will be determined. Based on the testing, a recom-
mendation will be made regarding the value of each of these systems
for this application, and future testing.
The objective of this task is to determine whether the Russian

melters can be used to immobilize spent nuclear fuel and selected
other waste streams.
Work Accomplished
The Diagnostic Instrumentation and Analysis Laboratory (DIAL)

at Mississippi State University has begun evaluation of a hybrid
plasma induction cold crucible melter (PICCM) for its potential suc-
cess in processing spent nuclear fuel and other heterogeneous, metal
containing waste. The hybrid plasma induction cold crucible melter
was developed at the Russian Institute of Chemical Technology in
Moscow. Though originally designed for producing chemically
active, high purity metals, it was brought to the United States for
research in treating radioactive wastes containing metal. The PICCM
combines plasma heating for the non-metal portion of the waste and
inductive heating for the metallic portion. A copper, water cooled cru-
cible is loaded with waste that upon processing contains distinct sep-
aration of metal from an upper layer of slag. Radioactive components
tend to concentrate in the slag phase which can be removed through
an over flow spout. The metal layer can be removed as an ingot for
DIAL 40395-1 72
reuse or for disposal as a low level waste. A simplified schematic is

shown in Figure 19. The cold crucible design nullifies the problem of
selecting/creating a refractory that can withstand glass and metal
environments in high temperature processing.40 The PICCM, fabri-
cated in Russia in 1994, was received at DIAL in May 1998 after a
brief installation at Georgia Tech during 1996. The potential for suc-
cess in this application supplies justification for immediate short term
as well as long term research opportunities for the international col-
laboration between the Russian developers and DIAL.
Plasma
Torch
Feed
Glass-Slag
Induction
Heating
Coils Metal Glass-Slag
Alloy Container
Cold Wall
Crucible
Extracation of Casting
FIGURE 19. Schematic of hybrid plasma induction cold crucible melter.
System Description
The PICCM is comprised of a melter vessel containing a 200-mm

diameter, water cooled crucible with individually isolated cooper seg-
ments. The crucible is designed with an overflow spout for removing
the slag layer during processing. The overflow spout drains into a
stainless steel bucket (approximate volume = 4 gal.) that is housed on
DIAL 40395-1 73
one side of the vessel. The bucket can be easily removed through a
door way on the side of the vessel by rolling it on the fold out tracks.
The vessel has a side port for off gas removal. Induction heating is
supplied by the water cooled copper coil wrapping the crucible. The
bottom of the crucible, also water cooled, is situated on a shaft that
moves up or down as directed by the DC motor/controller. The shaft/
crucible bottom combination is known as the ram. The melter vessel
is sealed on top with a cone-shaped lid. The lid has a small side view
port and port on top to accommodate the torch; it is equipped with a
rotary feeder. The feeder is activated with another DC motor/control-
ler.
Other items include a capacitor bank with eight capacitors of

which two are not used, four hydroblocks to control the delivery of
water to each water cooled elements in the system, an outside coil, a
draw sill, an induction power supply, a torch power supply and 70-
kW torch, and an operator console. The operating frequency is 2.4
kHz with a 480-V, 60-Hz source. The power limit for the melt opera-
tion is about 500 kW.
Experimental Set-up
The first of two technical exchanges between DIAL personnel

and Russian developers followed the PICCM arrival by approxi-
mately one month. The purpose of this meeting was to draft a plan for
the unit’s installation. Procurement and establishment of structural
and system support equipment at the new DIAL facility filled the
interim between the technical collaborations. Two Russian scientists,
Dr. Vitaliy Gotovchikov and Mr. Naum Gurvitch, visited DIAL near
the end of the reporting period for the second exchange (one month)
to complete installation and calibration of the PICCM.
Preparations began with a layout of equipment in the high bay

area for accommodating the PICCM and other test units at DIAL, a
combustion test stand and two plasma torches. Once the layout was
DIAL 40395-1 74
planned, the most immediate consideration became the design and

fabrication of a 20-ft x 20-ft platform to support the melter and its
water cooling units, the hydroblocks. The first technical exchange
resolved questions regarding the platform and optimization of space
in the high bay as well as provided a detailed plan for placement/ori-
entation of the melter vessel, power supply, capacitor bank, and
hydroblocks. The platform area was reduced to 18 ft x 18 ft and a
design was produced to utilize donated metal grating. Use of this
grating simplified the installation and reduced the labor required for
the water cooling connections made during the second exchange.
Placing the equipment on the platform prior to the developers’ arrival
allowed the necessary electricity supply, water supply, emergency
water supply, return water, and off gas piping installations to begin.
The equipment location and proximity to other objects were surveyed
for potential hazards; safeguards such as hand rails, warning signs,
and hard-hat only areas for the platform area and underneath were
constructed as needed.
Assembly of the PICCM began with the arrival of Dr. Gotov-

chikov and Mr. Gurvitch. Based on DIAL’s experience with plasma
torch operation, a decision was made to set-up the unit as an induc-
tion cold crucible melter (ICCM) and to explore top heating on an as-
needed basis. Using an ideal waste composition in the start-up phase
also diminishes the need for top heat. As a safety precaution, the
hydroblocks had been anchored to the platform grating. The melter
vessel sat on a 5/8-in. steel plate. Once the exact position was fixed, a
hole was cut in the plate beneath the crucible for the adjustable height
bottom (the ram) and water cooling lines to enter. Then the vessel was
bolted to the steel plate. The vessel was connected to the capacitor
bank through the outer coil, draw sill, and power supply cables to the
inner coil. With these items in place, the individual water lines, 56 in
all, to and from the hydroblocks were run. Other completed installa-
tions included the electricity supply, water supply, return water, emer-
gency water, and off gas piping.
DIAL 40395-1 75
The next phase of the ICCM installation was accomplished with

point by point evaluations of the power supply and water supply sys-
tems. Leak checks with emergency water flow (a lower flow rate)
were carried out first, then with the main water and return water
pumps activated. The operating water flow rate is approximately 160
gpm. The power supply was inspected for any damage or loose con-
nections resulting from shipping using a storage oscilloscope and a
megger. Control of the power supply would be carried out at the unit
because the torch and the operator console were eliminated from the
start-up assembly. The operator at the vessel would direct the power
settings from the platform area. A steel cylinder, 190-mm diameter
with an 8-mm wall thickness, was loaded into the crucible for a series
of quick burst calibrations. The ICCM was ready to begin processing.
Results and Discussion
The DIAL facility accomplished a tremendous amount of work to

get the Russian melter installed in a one-month period. Every request
for field fitting to enhance the assembly effort was quickly carried
out. For both the electricity and water, the work entailed getting the
supply to the melter area as well as making the necessary connec-
tions. It was, in general, a “from scratch” effort. Early on we experi-
enced a bit of the “new building” syndrome; the main water tank
could not be set until a concrete pad was poured, the water supply
lines could not be run until the university physical plant gave permis-
sion for going through the high bay wall, a main breaker was set at
half power which shutdown all power when the water system and
power supply were checked simultaneously, and there was a short in
the fluid cooler starting panel. Each difficulty was quickly worked
through. The most important lesson learned involved the air-cooled
heat exchanger; summer-like weather using this exchanger does not
cool process water to mimic expected Russian water temperatures.
Early morning runs could solve this problem combined with the fact
that most melter tests do not exceed 30 minutes.
DIAL 40395-1 76
Apart from the structural installation, several discussions and

mock training sessions were held. Start-up, operating, and shutdown
procedures were documented enabling DIAL personnel to operate the
system once the exchange ended. In addition to trouble shooting
guidelines, these procedures include the range of parameters for nor-
mal operation and upset conditions. Diagrams of the hydroblocks’
water cooling service to the various locations in the PICCM were
produced as a quick reference for trouble shooting. Almost all com-
munications took place through an interpreter.
Work Planned
•Perform melts with different combinations of metal and
borosilicate glass melts to condition the melter and train
operating personnel.
•Replace/repair items identified during the second exchange
(i.e., hoses on capacitor bank, cooling mechanism for Cu
bus bars, etc.)
•Develop operating procedures/historical data for various
materials (i.e., heterogeneous debris, simulated spent
nuclear fuel).
•Obtain thermal imaging of tests; measure particulate
(amount and identity) in the off gas.
•Upgrade electric, control, and water cooling systems by sup-
plying modern instrumentation and data collection.
•Investigate barriers to continuous operation; develop physi-
cal components and operating procedures to circumvent
those barriers.
References
40. Schumacher, R. F., et al. 1995. High-Temperature Vitrification of Low-

Level Radioactive and Hazardous Wastes. Savannah River Technology
Center.
DIAL 40395-1 77
Subtask 5.2. Hollow-electrode DC Arc Furnace

for Mixed-waste Treatment
Carlson C. P. Pian
Introduction
The hollow-electrode DC (HEDC) arc furnace is another

advanced melter concept which is more robust than current-genera-
tion furnaces. This technology could be considered for use on the
mixed wastes and orphaned spent fuel at the various DOE sites. The
plasma arc technology may also be used to destroy pesticide and
chemical weapon stockpiles.
The possible advantages of the hollow-electrode arc furnace for

nuclear waste remediation were discussed previously in Ref. 41.
HEDC arc furnaces are used commercially in the metals industries
with demonstrated service life of over many years without repairs.
The furnace electrodes are simple, inexpensive, and easily main-
tained. The simple electrode replenishment procedure is extremely
advantageous in the treatment of radioactive wastes since it does not
expose maintenance personnel to possible radiation hazards. Another
advantage of HEDC arc furnace is its ability to handle all forms of
wastes. Waste feeds can be in solid, liquid, and/or gaseous forms.
Work Accomplished
A feasibility study was carried out during this reporting period to

investigate the use of a hollow-electrode DC-arc furnace for the treat-
ment of mixed wastes. This test represents the first in a series of
planned tests.
DIAL 40395-1 78
Experimental Set-up
The initial feasibility test was conducted at Montec Associates in

Butte, MT, using an existing plasma torch furnace. The decision to
test at Montec was based on several factors. They have in place a DC
power supply capable of providing the high amperage (1250 amps)
necessary to evaluate the electromagnetic effects that makes the hol-
low-electrode arc heating concept for waste remediation unique.
Moreover, Montec has a plasma test cell that is suited for these tests,
which would not require major modifications. They also had the
capability for mounting the arc electrode assembly and for control-
ling its position.
NITROGEN
FEEDER
AIR
DILUTION
E
NC
HOLLOW ELECTRODE
LA
PITOT MEASUREMENT
COOLANT OUT
FLOWMETER
OFF GAS
COOLANT IN
THERMOCOUPLE (TYPE K)
FLOW
PRESSURE
FIGURE 20. DC arc furnace at Montec Associates, Butte, MT.
The arc furnace is shown in Figures 20 and 21. The test vessel
consisted of a water-cooled steel dome, which is four feet in diameter.
The hollow graphite electrode, eight inches in diameter, extends into
the furnace through a port at the center of the dome. The lumen (inner
passage) of the electrode was four inches in diameter. The feed mate-
rial was delivered directly into the lumen at a controlled feeding rate
by an auger-type feeder, positioned above the electrode. This feeder,
DIAL 40395-1 79
shown in Figure 22, had a capacity for about 100 pounds of solid
feed. The electrode and the feed system was mounted on a platform
above the furnace. A roof-mounted crane/pulley system was used to
raise and lower this platform, which in turn adjusts the height of the
electrode relative to the melt surface.
FIGURE 21. DC arc furnace at Montec Associates,

Butte, MT, July 1998.
DIAL 40395-1 80
FIGURE 22.Feeder for the hollow-electrode DC arc heater experiment,

Montec Associates, Butte, MT, July 1998.
FIGURE 23. Hollow-electrode dc arc heater at Montec Associates,

Butte, MT, July 1998.
DIAL 40395-1 81
An alternate lance feed system was also used during our test. An
auxiliary port on the furnace dome was used for the lance feeder (see
Figure 20). The purpose of this feeder was to provide baseline data
(for the conventional method of dropping the waste materials into the
melt) that could be used to compare with the new method of deliver-
ing the charge directly into the plasma arc.
The furnace bottom consists of several layers of refractory brick,

as shown in Figure 20. A simple steel anode design was used in our
initial feasibility test for cost and material availability reasons. This
anode consisted of a water-cooled circular base, 12 inches in diame-
ter. Thin steel strips (fins) were welded onto the top surface of the
electrode base and used as conducting paths for the electric current.
The spaces between the bricks, and between the electrode fins were
filled with a refractory ramming compound. This particular anode
design configuration provided adequate lifetime (over 12 hours) for
the initial feasibility tests. An anode design which uses conducting
refractory material that does not require water cooling will be
required for longer test durations or for actual waste processing appli-
cations.
Ports in the off-gas line were used for gas sampling and for pitot-
tube velocity measurements. Gas analyzers used in our test consist of
a micro fuel cell oxygen analyzer, two dual carbon dioxide/carbon
monoxide nondispersive infrared analyzers (for different concentra-
tion ranges of each species), and a total hydrocarbon analyzer. During
certain segments of our test, an iso-kinetic sampling train was used to
determine the particle concentration in the off-gas stream. Down-
stream of the sampling ports, an existing scrubbing device at Montec
was used to clean and quench the exhaust gas.
The heat-up period for each furnace test typically lasted about
three to four hours. Initially, the furnace bottom was loaded with a
layer of soil (about six to ten inches deep). To initiate the arc, a pile of
scrap iron was positioned above the anode to provide a current path.
DIAL 40395-1 82
The furnace operates initially in a joule-heating mode with the graph-

ite electrode in direct contact with the soil/iron scraps. As the soil was
heated up and began to melt, the graphite electrode was raised to
establish the plasma arc. During the heat-up period, additional soil
was added to the furnace until a deep pool of melt is obtained. Figure
23 shows a view of the hollow electrode through the viewing port
after the power was turned off.
25 1400
O2 (%)
Potatoes
CO2 (%)
CO (ppm) 1200
20
Oak Blocks
Species Concentration (molar %)
Species Concentration (ppm)

1000
15
800
600
10
Brickettes
400
200
Brickettes
Bulk Addition
Through Lumen Bulk Addition Through Lance
0 0
12:45 12:50 12:55 13:00 13:05 13:10 13:15 13:20 13:25 13:30
Time (h:m:s)
FIGURE 24. Off-gas species concentration during bulk-solid addition, Montec

Associates, Butte, MT, August 1998.
A substantial amount of dust was generated by the plasma arc

during the heat-up period. The interior surfaces of the furnace and
exhaust pipe were coated with a thick build-up of white powder. The
composition of this dust was later analyzed and found to consist
largely of silicon. The dust quickly clouded the quartz view-port win-
dow and caused considerable plugging problems for the gas sampling
DIAL 40395-1 83
probes, resulting in decreased sampling time. Dust generation ceased

once a melt of sufficient depth was established within the furnace.
Preliminary Results
One of the advantages of the HEDC arc furnace for treating

wastes is its ability to handle fines. Fine grain materials can be fed
directly without prior briquetting. The arc at the tip of the cathode
acts as a continuation of the electrode/feeder cylinder and directs the
flow of feed into the melt. Dust particles and untreated wastes are
entrained into the bath thus avoiding carryover of particulates into the
off-gas treatment system. To demonstrate this attribute of HEDC arc
furnace in our test, alumina powder was fed into the furnace, first
through the lumen, and later through the lance at the same feed rate,
in order to determine if there was any difference in the off-gas dust
loading between the two feeding methods.
Gas samples were collected with an EPA Method 5 sampling train

to determine the off-gas particle concentrations. Due to the limited
test times, only three samples were collected: two samples during the
period when alumina powder was fed through the lumen, and one
during the period when feeding was through the lance. Analysis of
the data indicated that particle concentration in the off gas decreased
with increasing furnace operating time, and that the collected powder
was mostly silicon. This appears to be an artifact of the initial period
of silica dust generation and suggests that we might have initiated the
alumina injection test before an adequate melt was established. As
mentioned previously, dust generation from arc vaporization of the
soil can be a problem prior to achieving a sizable melt in the furnace.
Another advantage of the HEDC arc furnace for treating wastes is

its ability to deliver the charge directly into the arc, resulting in very
efficient arc heat transfer to the charge material. Also, when the feed
materials are funneled through the hollow electrode, the cathode arc
acts like a pump, pushing the materials downward and ejecting them
DIAL 40395-1 84
towards the anode and into the melt. This acceleration force arises
from the Maecker effect.42,43 To evaluate these attributes of the HEDC
arc in our test, we compared the thermal treatment of bulk wastes
using the HEDC arc feeder with that using a lance feeder. Three dif-
ferent forms of bulk wastes were tested: whole potatoes, blocks of
wood (oak), and “heterogeneous debris” briquettes. The potatoes
were about 1.5 to 2 inches in diameter. The oak blocks were about 1.5
inch squares. The briquettes were “pillow-shaped,” and have dimen-
sions of about 2” x 1.2” x 0.75”. The ingredients of the briquettes
were a mixture of approximately equal parts of PVC granules, pecan
shell fines, glass beads, iron powder, Perlite, and alumina powder. A
small amount of starch was used as binder material.
The bulk-solid addition tests were carried out twice, once with the
furnace view port opened for video taping and once with the port
sealed for off-gas analysis. The visual observations portion of the test
clearly showed that objects fed through the lumen were accelerated
by the Maecker effect and thrusted into the melt. In some cases the
objects appeared to have been shattered after they entered the melt. In
other cases, the objects remained intact and were burned up at the arc/
melt interface. When the bulk solids were dropped through the lance,
most of them came to rest on the crusty slag layer above the melt,
where they were heated from below and slowly burned up. In few
instances, the objects broke the slag crust and floated on the surface
of the melt.
The off-gas analysis also indicated more efficient thermal treat-

ment of the bulk-solid wastes fed through the HEDC arc. Figure 24
shows the time variation of off-gas species concentrations during the
bulk-solid addition portion of the test. Bulk addition through the
lumen occurred between 12:53 and 13:03; and through the lance
feeder between 13:08 and 13:26. Spikes in CO and/or CO2 concentra-
tions and dips in O2 concentrations indicate times when objects were
introduced into the furnace. Generally a group of five to seven objects
were introduced at a time. The durations of the concentration spikes
DIAL 40395-1 85
(or dips) suggest that objects fed through the lance took about five
times longer to process than when they were fed through the lumen.
The low CO concentration and high O2 levels measured prior to 12:55
may have been caused by an opened furnace port.
FIGURE 25. Dissolution of the refractory bricks. Hollow-electrode

are furnace tests, Butte, MT, August 1998.
This test was terminated after about 13 hours of operation, due to

a containment failure in the brick bottom. At the time of the failure,
preparations were underway to initiate a test segment to evaluate
HEDC arc furnace’s ability to thermally treat soil contaminated with
diesel fuel. The failure of the brick containment was due to dissolu-
tion of the refractory bricks by the high temperature melt. Figure 25
shows a cross-sectional view of the damaged bricks.
Lessons learned from our HEDC arc furnace test are summarized
in Table 7. The test data indicate that treatment of bulk-solid wastes
can be carried out much more efficiently in the HEDC arc furnace
than in the conventional DC-arc or plasma-torch furnaces.
DIAL 40395-1 86
TABLE 7. Lessons learned (preliminary).

•Arc characteristic and stability are strong function of elec-
trode polarity.
•Hollow cathode results in more stable arc.
•Hollow anode results in simpler bottom electrode design.
•Need to design furnace bottom (anode) without the necessity
for water cooling.
•Need to analyze acid/base characteristics of melt and refrac-
tory bricks and address their compatibility.
•Overheating of melt can be a problem in shallow melt pools
and during heat-up periods - leading to dust generation.
•Limited data suggesting feeding through lumen can result in
faster and more complete thermal treatment of bulk
wastes.
Work Planned
Future tests are planned to accomplish the following:

•Complete unfinished portion of test plan: diesel fuel laden
soil and Method 29 off-gas sampling.
•Anode redesign without water cooling.
•Redo alumina dust segment of experiment with soil/alumina
mixture.
•Determine effect of submerged electrode (dipped into melt)
on dust generation and melt heating.
•Characterize off-gas as a function of melt chemistry.
•Quantify factors affecting off-gas dust loading. Pool size of
melt, melt chemistry, arc power, and soil feed rate can all
affect dust loading in exhaust.
DIAL 40395-1 87
•Quantify Maecker effect. Six-inch diameter lumen, vary

magnitude of arc current, video/laser imaging of particles
flowing through arc.
•Measure temperature of melt.
References
41. Plodinec, M.J., et al. 1998. Application of Modern Diagnostic Methods to

Environmental Improvement. Final Report to U.S. Department of Energy,
Contract No. DE-FG02-93CH-10575, Reporting period July 30, 1993 -
March 31, 1998. Mississippi State University: Diagnostic Instrumentation
and Analysis Laboratory.
42. Maecker, H. 1995. Plasma Streaming in Arcs Due to Self-Magnetic Com-

pression. Z. fur Physik (in German) 141:198-216.
43. Pfender, E., et al. 1987. Plasma Technology in Metallurgical Processing, J.

Feinman, Editor, Iron and Steel Society, Inc., Ch. 4, pp. 32-33.
DIAL 40395-1 88
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Laser-induced breakdown spectroscopy (LIBS)

Article in Analytical and Bioanalytical Chemistry · May 2011

Jagdish P Singh Jose Almirall

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Geochemical Fingerprinting of Heroin View project

The user has requested enhancement of the downloaded file.

Quarterly Technical Progress Report

Dr. John Plodinec, Principal Investigator

Prepared for the U.S. Department of Energy

Diagnostic Instrumentation and Analysis Laboratory

TASK 1 Verification Monitors for Thermal

TASK 2 Deactivation and Decommissioning

DIAL 40395-1 iii

TASK 3 Technical Data to Support Cleanup

TASK 4 Product Acceptance Support . . . . . . . . . . . . . . 56

TASK 5 Advanced Cleanup Support:

FIGURE 1. Schematic of APO-GEM continuous emission

FIGURE 11. Comparison of experimental and predicted results

TABLE 1. Detection limits for the APO-GEM for various

DIAL 40395-1 vii

The Diagnostic Instrumentation and Analysis Laboratory (DIAL), an

As part of this program, diagnostic methods are developed and evalu-

Moreover, on-site field measurements at various DOE facilities are

In addition to the diagnostic instrumentation development efforts,

Subtask 1.1. Monitors for Thermal Processes

Thermal treatment processes (incinerators, melters) typically emit

During the first year of the Cooperative Agreement, DIAL will

Personnel from the major thermal treatment process operators in

The objective of this subtask is to determine, through testing,

Air Plasma Off-gas Emission Monitor (APO-GEM)

Increasing regulatory demands requiring significant reductions in

The introduction of exhaust gases into the air plasma results in a

The remaining hardware required to complete the system consists

The APO-GEM system incorporates a novel 3.5-kW solid-state

DETECTOR AIR-PLASMA ISOKINETIC

CONTROLLER rf POWER NEBULIZER

FIGURE 1. Schematic of APO-GEM continuous emission monitor.

The APO-GEM plasma is started using argon and progressively

In addition, we are evaluating a novel solid-state spectrometer

Isokinetic sampling system. To correctly measure the concentration

Calibration. An important concern with any CEM is the question

where CA is the aerosol concentration (x 103 µg/m3), Cs is the stan-

To further improve the sensitivity of the instrument, a novel

regions of interest was collected during the shakedown period prior to

Detection limits. The toxic metal species of concern to EPA and

Metal Detection Limits

TABLE 2. Relative accuracy of DIAL Air-ICP data.

Metal concentrations and relative accuracy. The

Results and Discussion

The field trip late last year to participate in the DOE/EPA-spon-

Air plasma parameters. A laboratory study characterizing the

Chamber temperature effect on Mg II/Mg I

Chamber temperature effect on Mg II/Mg I

Chamber temperature effect on Mg II emission

FIGURE 2.The effect of moisture on the emission of Mg in an

Sampling interface. Modifications to the isokinetic sampling system

An evaluation of high resolution AOTF-echelle

A week-long test of this instrument occurred at DIAL in August

A paper was presented at the ACS 215th national meeting, Dallas,

Intensity (arb. units)

228.76 228.80 228.84 309.95 310.00 310.05 310.10

FIGURE 3. ICP emission spectra obtained using the AOTF-echelle