1. Radiochemistry Center of Excellence
Expanding the Horizons of Nuclear Forensics
Analysis
John D. Auxier II
University of Tennessee
Nuclear Engineering Colloquium
January 21, 2015 -- Knoxville, TN
2. The context
§ Importance of training nuclear and
radio-chemists
§ Nuclear Melt Glass
§ Gas-phase separations
4. What is a radiochemist?
ORNL
Physics
Division
NIST
Radiochemist:
one
who
uses
the
radioac#ve
nature
of
ma=er
to
study
non-‐radioac#ve
proper#es
of
reac#ons
Nuclear
chemist:
one
who
uses
chemistry
to
study
radioac#ve
elements
5. Studies of the pipeline
§ 1978: The American Chemical Society’s (ACS) Division
of Nuclear Chemistry and Technology (DNCT) first
noted a decline in nuclear and radiochemistry faculty
and students in chemistry departments
§ 1988: National Research Council, Training
Requirements for Chemists in Nuclear Medicine,
Nuclear Industry, and Related Areas.
§ 2004: DOE/NSF Nuclear Science Advisory Committee,
Education in Nuclear Science
§ 2008: AAAS/APS, Nuclear Forensics: Role, State of the
Art, Program Needs
§ 2012: National Research Council, Assuring a Future
U.S.-Based Nuclear Chemistry Expertise
6. numbers of degree holders in this discipline.
Nuclear and radiochemistry needs cannot simply be filled by transfers
from the larger groups of engineering and physics degree holders. Much of
the chemistry involved in separating actinides, preparing reagents for nuclear
medicine, and removing radioactive materials from the environment requires
knowledge of synthetic, analytical, and other aspects of chemistry, informa-
1-2.eps
0
50
100
150
200
250
1950
1953
1956
1959
1962
1965
1968
1971
1974
1977
1980
1983
1986
1989
1992
1995
1998
2001
2004
2007
NumberofEarnedDoctorateDegrees
Academic Year
Nuclear chemistry
Nuclear physics
Nuclear engineering
FIGURE 1-2 Number of Ph.D.s per year in selected nuclear science and engineering
disciplines, 1950–2007.
NOTE: Survey of Earned Doctorates stopped counting nuclear chemistry degrees after
2003.Assuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
US nuclear chemistry PhD’s
7. Radchem PhD’s (keyword based)
DEFINING NUCLEAR AND RADIOCHEMISTRY EXPERTISE 21
2-1.eps
0
5
10
15
20
25
30
35
40
45
1970 1975 1980 1985 1990 1995 2000 2005 2010
Count
Year
SED Ph.D. Degrees
PQDT Ph.D. Theses
FIGURE 2-1 U.S.-granted Ph.D. degrees and dissertations in nuclear chemistry by year,
1970-2010, based on the National Science Foundation Survey of Earned Doctorates
(SED) and the ProQuest Dissertation and Theses (PQDT) database. SED data (blackAssuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
8. US peer-reviewed contributions in
radiochemistry declining
24 ASSURING A FUTURE U.S.-BASED NUCLEAR AND RADIOCHEMISTRY EXPERTISE
2-4.eps
0%
10%
20%
30%
40%
50%
60%
70%
80%
1970
1972
1974
1976
1978
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
2008
2010
%U.S.Authorship
Publication Year
Uranium
Plutonium
Technetium
Thorium
Fluorine-18 or (18)F
FIGURE 2-4 Percentage of U.S.-authored papers out of the total number of papers for
selected keywords, 1970-2010.
SOURCE: Web of Science keyword search, http://apps.webofknowledge.com, Septem-Assuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
9. Nuclear Eng. PhD’s trending up
ASSURING A FUTURE U.S.-BASED NUCLEAR AND RADIOCHEMISTRY EXPERTISE
2-2.eps
0
20
40
60
80
100
120
140
160
180
200
1970
1972
1974
1976
1978
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
2008
2010
NumberofNuclearEngineeringPh.D.DegreesAwarded
Year
FIGURE 2-2 Trend in nuclear engineering Ph.D. degrees, 1970-2010.
NOTE: Includes programs with nuclear engineering majors and option programs inAssuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
10. Faculty base was a concern
§ 2008: 46 active faculty identified
– Across 20 universities
– Producing 114 PhD’s
– 7 universities were “singlets”
– 5 universities were “doublets”
– Largest program was Washington
University in St. Louis, with 6 faculty in
nuclear medicine program
Assuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
11. Additionally, academic radiochemistry
programs face significant challenges
§ Perceived risk
§ Expense of compliance
§ Lack of faculty base
§ General shift from experimental
science to modeling and simulation
§ Increasing challenges using the
national labs
§ Budgets and budget cycles
Assuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
12. 2012: Findings
§ Faculty base was extremely vulnerable
§ Little or no undergraduate curricula
§ Programs with only one faculty were
unsustainable
§ Funding was limited and unpredictable
§ Data sources for tracking the academic
health of the field are poor or missing
§ Specific programs were helping, but not
fast enough
Assuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
13. Overall conclusions – Demand
and Supply
(5-‐year
data)
BS
MS
PhD
Demand
200
93
306
Supply
250
50
65
Assuring
a
Future
U.S.-‐Based
Nuclear
Chemistry
Exper=se,
Na#onal
Research
Council
(2012)
14. In memoriam,….
W.
Frank
Kinard
(2013)
College
of
Charleston
Heino
Nitsche
(2014)
University
of
California
15. And one last bit of bad news
§ Update on the Nuclear Chemistry
Summer Schools
§ From NUCL Newsletter: This is traditionally the time of year
that we announce the dates for the summer schools. I regret to
inform the Division that at this time we have not received
any funding for the fourth year of the five year grant
that will allow us to hold the summer schools in
2015.
DNCT
NewsleIer,
October
2014
19. Motivation
§ Lack of available nuclear melt glass
§ Development of analytical techniques
needed
§ Support of radiochemistry and nuclear
forensic education
20. Event
Environmental
Knowns
Post
Material
Analysis
Regional
Produc#on
Comparison
A=ribu#on
Scenario
Selec#on
Es#mates
of
Environment
Develop
Surrogate
Produce
Event
Surrogate
Sample
Analysis
Surrogate
Material
Regional
Produc#on
Comparison
Verifica#on
&
Valida#on
Applica#on
Laboratory
22. Development and Synthesis
§ Trinitite used as a
benchmark
§ Powdered oxides used
to create sample
matrix
§ Matrix melted and
vitrified
STF Composition (by mass fraction)
Trinitite Data Synthetic Formulation
Comp. Fraction Comp. Fraction
SiO2 6.42x10-1
SiO2 6.42x10-1
Al2O3 1.43x10-1
Al2O3 1.43x10-1
CaO 9.64x10-2
CaO 9.64x10-2
FeO 1.97x10-2
FeO 1.97x10-2
MgO 1.15x10-2
MgO 1.15x10-2
Na2O 1.25x10-2
Na2O 1.25x10-2
K2O 5.13x10-2
KOH 6.12x10-2
MnO 5.05x10-4
MnO 5.05x10-4
TiO2 4.27x10-3
TiO2 4.27x10-3
U 1.60x10-5
UNH 3.37x10-5
Total 9.81x10-1
Total 9.91x10-1
Element Fraction Element Fraction
Si 3.00x10-1
Si 3.00x10-1
Al 7.55x10-2
Al 7.55x10-2
Ca 6.88x10-2
Ca 6.88x10-2
Fe 1.53x10-2
Fe 1.53x10-2
Mg 6.90x10-3
Mg 6.90x10-3
Na 9.24x10-3
Na 9.24x10-3
K 4.26x10-2
K 4.26x10-2
Mn 3.93x10-4
Mn 3.93x10-4
Ti 2.58x10-3
Ti 2.58x10-3
O 4.60x10-1
O 4.69x10-1
U 1.60x10-5
U 1.60x10-5
N 0 N 1.88x10-6
H 0 H 1.10x10-3
27. Gamma Spectroscopy (Cont.)
Nuclide ROI Half-‐Life
(yr)
Energy
(keV)
Branching
RaPo
(%)
Act.
(Bq/g
)
-‐
TriniPte
Act.
(Bq/g
)
–
STF
133Ba1,2,3 5 10.51 356.01 62.05 27.1 ± 0.5 N/A
137Cs1,2,3 8 30.05 661.66 84.99 32.1 ± 0.04 N/A
152Eu1,2,3 3 13.522 121.7 28.41 69.9 ± 0.8 N/A
4
334.2 26.59
10
778.9 12.97
11
964.08 14.50
154Eu1,2,3 * 8.601 123.07 40.40 158 ± 0.4 477 ± 9.3
9
723.3 20.05
12
1,004.7 17.86
13
1,274.4 34.90
155Eu1 * 4.573 86.55 30.7 0.9 ± 0.6 0.38 ± 0.003
*
105.31 21.1
239Pu1 1 24.1x103 51.62 0.02 11208 ±
3907
N/A
*
129.30 0.002
6
375.05 0.0015
7
413.71 0.0015
241Pu2 * 14.35
103.68 1.0E-‐4 63.0 ± 1.8 N/A
241Am1,2,3 2 432.2 59.94 35.92 13 ± 11 N/A
60Co1,2,3 * 5.271 1,173.2 99.85 44 ± 4 N/A
*
1,332.4 99.98
95Zr
is
the
actual
isotope
126Sn
is
the
actual
isotope
1P.
P.
Parekh
et
al.,
“Radioac#vity
in
trini#te
six
decades
later.,”
J.
Environ.
Radioact.,
vol.
85,
no.
1,
pp.
103–20,
Jan.
2006
2J.
J.
Bellucci
et
al
,
“Distribu#on
and
behavior
of
some
radionuclides
associated
with
the
Trinity
nuclear
test,”
J.
Radioanal.
Nucl.
Chem.,
vol.
295,
no.
3,
pp.
2049–2057,
Sep.
2012
3D.
Schlauf,,et
al“Trini#te
redux:
Comment
on
‘Determining
the
yield
of
the
Trinity
nuclear
device
via
gamma-‐ray
spectroscopy,’”
Am.
J.
Phys.,
vol.
65,
no.
11,
p.
1110,
1997.
28. Synthetic Trinitite Results/Conclusions
§ It is possible to produce melt glass that is
similar to trinitite in:
– Elemental Composition
– Morphology
– Radiological Signature
– Chemical Behavior
§ This melt glass can be used as a viable surrogate for
radiochemistry/ nuclear forensic applications
29. Background
§ Separations are important part of
nuclear forensics.
– Post-Detonation Scenarios1
– Current liquid methods are time-
consuming
§ Need for Rapid Separations
– Experiment with gas chromatography/
mass spectrometry separations2 for
thermochemical separations3
1Development of Synthetic Nuclear Melt Glass for Forensic Analysis” Molgaard, Auxier et. al.
J. Rad. Nucl. Chem., 2015, In press.
2 “Assessing thermochromatography as a separation for nuclear forensics: current capability
vis-a-via forensic requirements”, Hanson et. al 2011, J. Rad. Nucl. Chem.
3Synthesis and detection of a seaborgium carbonyl complex, Even et al., 2014, Science,
30. Background (Cont.)
§ Ligands for ease of volatilization and
rapid separation
1,1,1,5,5,5
–
hexafluoro
–
2,4
–
pentadione
(denoted
hfac)
6,6,7,7,8,8,8-heptafluoro-2,2-
dimethyl-3,5-octanedione (denoted hfod)
2,2,6,6-‐tetramethyl-‐3,5-‐
heptanedione
(denoted
hdpm)
31. Outline
§ Ligand Synthesis
– Comparison in terms of timeliness and
percent yield.
– Mass Spectrometry Analysis
§ Separations
– Mass Spectra
– Time separated separations
§ Conclusions
32. Rapid Separations Flowchart
Dissolve Ln oxides
use of HCl, HNO3,
H2SO4
Prepare NH4[ligand]
Hhfac + NH4OH à
NH4[hfac] + H2O
Combine NH4[hfac] with LnCl3
X NH4[lig] + LnCl3 à Ln[hfac]x + X NH4Cl
Extract Ln[hlig]4 into
organic phase and dry
Structural Characterization and
Purity Determination:
FT-ATR-IR (NDA), P-XRD (NDA),
SC-XRD (~ 5 mg), ICP-TOF-MS (~1
mg), MP (~2 mg), NMR (~1 mg)
Separate using
thermochromatographic
methods.
34. Synthesis of Ln[hfac]4 Compounds
Compound
%
Yield
Sm
35.0-‐36.3
Gd
57.9-‐60.0
Tm
57.2-‐59.2
1Sievers, R. E.; Ponder, B. W.; Morris, M. L.; Moshier, R. W. Inorganic Chemistry 1963, 2, 693.
2Eisentraut, K. J.; Sievers, R. E. Journal of the American Chemical Society 1965, 87, 5254.
3Springer, C. S.; Meek, D. W.; Sievers, R. E. Inorganic Chemistry 1967, 6, 1105.
35. Synthesis of Ln[hfod]x compounds
Compound
%
Yield
Nd
21.0-‐21.6
Sm
15.8-‐16.2
Dy
14.3-‐14.7
1Sievers, R. E.; Ponder, B. W.; Morris, M. L.; Moshier, R. W. Inorganic Chemistry 1963, 2, 693.
2Eisentraut, K. J.; Sievers, R. E. Journal of the American Chemical Society 1965, 87, 5254.
3Springer, C. S.; Meek, D. W.; Sievers, R. E. Inorganic Chemistry 1967, 6, 1105.
48. Separation Efficiency
§ Resolution
– Equation: ∆tr/wav > 1.5
• ∆tr is the difference in retention times for two
compounds
• wav is the average base of the same two peaks
– Separation largely based upon physiosorption
interactions
• Driven by the ΔHabs and ΔHdes of the individual
compounds.
• These entropic factors will be used to model separation
parameters
49. Comparison of Separation
Efficiency
Ln[hfac]4
Compounds
ResoluPon
(∆tr/wav )
Sm
and
Tm
3.25
Tm
and
Nd
5.30
Ln[hfod]x
Compounds
ResoluPon
(∆tr/wav )
Nd
and
Sm
No
separa#on
Sm
and
Dy
No
separa#on
Ln[hdpm]x
Compounds
ResoluPon
(∆tr/wav )
Pr
and
Eu
7.43
50. Conclusions
– Successfully synthesized and characterized
• 14 of the Ln[hfac]4·NH4 compounds
• 14 Ln[hfod]x compounds
• Pr, Eu, and Ho hdpm compounds
– Have made initial measurements as to separation
thermodynamics
• Used Electron Ionization Mass Spectrometry
– Have begun to make progress in separations with the first
ever GC-ICP-TOF-MS system
• Initial results are promising
51. Future Work
§ Radiochemistry Center
– Continue to recruit undergraduate and graduate students
for the program
– Develop useful curricula for nuclear and radiochemistry
students
§ Melt Glass
– Begin to distribute samples to National Labs and other
universities
– Begin to make urban nuclear melt samples
§ Advanced Separations
– Make first thermodynamic separation measurements of
these compounds
– Finalize dissolution techniques to aid melt glass analysis
52. Publications from related work.
§ J. D. Auxier II, S. A. Stratz, D. E. Hanson, M. L. Marsh, H. L. Hall
“Synthesis and Characterization of Lanthanide 6,6,7,7,8,8,8-Heptafluoro-2,2-
Dimethyl-3,5-Octanedione Complexes” Under Review Inor. Chem.
§ J. J. Molgaard, J. D. Auxier II, C. J. Oldham, M. T. Cook, H. L. Hall,
“Development of Synthetic Nuclear Melt Glass for Forensic Analysis” J. Rad.
Nucl. Chem. 2015 In Press
§ A. V. Giminaro, S. A. Stratz, J. A. Gill, J. P. Auxier, C. J. Oldham, M. T. Cook,
J. D. Auxier II, J. J. Molgaard, H. L. Hall, “A Method for Development of
Synthetic Urban Nuclear Melt Glass for Rapid Forensic Analysis” Under
Review to J. Rad. Nucl. Chem.
§ 4 others in process
§ Also sponsored the Radiobioassay and Radiochemical Measurements
Conference, Knoxville, TN 2014
53. Patents in Process from related
work
§ J. J. Molgaard, J. D. Auxier II, H. L. Hall, “Novel Synthetic
Nuclear Melt Glass and Methods Thereof” 2014, Pat. Pend.
62/002,202
– Also: A. V. Giminaro, C. J. Oldham, Mr. J. P. Auxier, E. K. Fenske, J. D.
Auxier II, H. L. Hall, “Standard Testable Urban Formation for Forensics
(S.T.U.F.F.)”, 2014 has been combined in the license
§ J. D. Auxier II, D. E. Hanson, M. L. Marsh, H. L. Hall, “Gas-
phase Thermochromatographic Separations of Fission and
Activation Products”, 2014, Pat. Pend. 62/028,199
§ S. J. Willmon, H. L. Hall, J. D. Auxier II, Ms. Hannah Hale, M.
Thornbury, “Broad Area Search Bayesian Processor” 2015 Under
Review
§ J. D. Auxier II, J. Stainback IV, M. T. Cook, M. J. Willis, J. D.
Birdwell, R. Horn., “Radiation Detection Instrumentation
Universal Simulator (RADIUS)”, 2014, Pat. Pend. 62/033,821
§ M. T. Cook, A. V. Giminaro, D. E. Hanson, J. D. Auxier II, H. L.
Hall, “Solid Sample Introduction System for Gas
Chromatography” 2014, Under Review
54. Collaborators (Hall Group)
§ Melt Glass
– Joshua Molgaard (M.S. – now at USMA)
– Andrew Giminaro, Jerrad Auxier, Jonathan
Gill, CJ Oldham, Matthew Cook
§ Advanced Separations
– Daniel Hanson (now Ph.D. at SRNL)
– Adam Stratz, Steven Jones (Bredesen
Scholar)
– UGS: Matthew Marsh (ACS Coryell Award
Winner), Ashlyn Jones
55. Interdepartmental Collabotors
§ UT Chemistry: Derek Cressy, Derek Mull,
Dr. David Jenkins, Dr. Carlos Steren
§ Materials Science Engineering: Dr.
Stephen Young
§ UT/ORNL Joint Institute for
Computational Sciences: Dr. Deborah
Penchoff
56. RCoE impact on the UT academic
program
§ Radiochemistry Certificate program
§ Nuclear Engineering’s Nuclear Security
curricula
§ New NE building programming
§ Funding: U.S Dept. of Energy, National
Nuclear Security Administration, Scientific
Stewardship Academic Alliances Program
– Special Thanks to Dr. Howard Hall and Dr.
Lawrence Heilbronn
60. Elemental Analysis
Compound Element Theory
(%) Found
(%)
La[hfac]4
-‐*
X
H2O
C 23.55 24.7
H 1.28 1.31
N 2.93 2.65
F 47.75 43.41
Gd[hfac]4
-‐*
X
H2O
C 23.54 24.35
H 0.99 0.96
N 2.75 2.95
F 44.69 42.74
Lu[hfac]4
-‐*
X
H2O
C 23.44 23.62
H 0.79 0.78
N 1.71 1.63
F 44.5 42.09
• Possible residual NH4R, causing differences in F %
• Possible hydration differences causes differences in
hydrogen amounts
62. Elemental Analysis hfod
Compound Element Theory Found
C 30.46 31.54
H 2.9 2.91
N 0 0
F 33.72 32.73
C 34.56 34.99
H 3.34 3.515
N 1.01 1.035
F 38.27 38.47
C 34.13 34.585
H 3.29 3.235
N 1 1.045
F 37.79 38.16
La[fod]3
*2H2O
NH3
+
(Gd[fod]4
-‐
)
*2H2O
NH3
+
(Lu[fod]4
-‐
)
*2H2O
*A
4:1
mole
ra#o
of
NH4[fod]:LnCl3
was
used.
*One
possible
product
from
this
would
be
the
charged
8-‐coordinate
dihydrate
(NH3+
[Ln(Hfac)4
-‐]*2H20).
*The results go against
expectation that the
smaller cations would
have less ligands
63. Sm Gd Ho
FuncPonal
Assignment*
741
741
741
C-‐CF3
stretch
806
804
821
C-‐H
out
of
plane
bend
1117
1117
1117
C-‐H
in-‐plane
bend
1178
1178
1178
C-‐F
stretch
1220
1220
1220
C-‐F
stretch
1276
1276
1276
C-‐F
stretch
1458
1458
1458
C-‐H
bend,
[Hfac]-‐
metal
coordina#on
1509
1509
1509
C-‐O
stretch,
C-‐H
bend,
[Hfac]-‐metal
coordina#on
1593
1593
1593
C=C
stretch,
[Hfac]-‐
metal
coordina#on
1624
1624
1624
C-‐O
stretch,
[Hfac]-‐
metal
coordina#on
2974
2974
2974
O-‐H
stretch
Ln[hfod]x FT-ATR-IR Results
65. NMR Results Ln[hfod]x (cont’d)
La
Gd
Lu
Legend
*Shows
most
varia#on
across
series
due
to
being
metal
coordina#on
site
*Larger
ionic
radius
coordina#on
→
greater
shiq
upfield
*ParamagnePc
properPes
causes
large
shiqs
and
line
broadening
=
lower
quality
NMR
results
66. FT-IR Results hdpm
Hdpm Eu Pr FuncPonal
Assignment*
741
760
759
C-‐H
out
of
plane
bend
797
793
793
C-‐H
out
of
plane
bend
874
867
867
C-‐H
bend
1133
1130
1130
C-‐H
in
plane
bend
1220
1220
1220
C-‐O
stretch
1365
1380
1350
C-‐H
rock,
[Hdpm]
metal
coordina#on
1604
1500
1490
C-‐O
stretch,
C-‐H
bend,
[Hdpm]
metal
coordina#on
1604
1570
1570
C=C
stretch,
[Hdpm]
metal
coordina#on
3198
2950
2950
C-‐H
stretch
____
[Hdpm]
100
0
50
Wavenumbers
cm-‐1
67. Elemental Analysis hdpm
Compound Element Theory Found
C 30.46 31.54
H 2.9 2.91
C 34.13 34.585
H 3.29 3.235
Eu[dpm]3
Pr[dpm]3
*A
3:1
mole
ra#o
of
Na(dpm):LnCl3
was
used.
*Steric
hindrance
of
t-‐butyl
groups
influences
Ln[dpm)3]
product.
