NONPROLIFERATION	
  AND	
  NUCLEAR	
  
FORENSICS:	
  DETAILED,	
  MULTIANALYTICAL	
  
INVESTIGATION	
  OF	
  TRINITITE	
  POST-­‐
DETONATION	
  MATERIALS	
  
Antonio	
  Simonetti	
  
Dept.	
  Civil	
  &	
  Environmental	
  Engineering	
  &	
  Earth	
  Sciences	
  
University	
  of	
  Notre	
  Dame	
  
University	
  of	
  Notre	
  Dame-­‐
TEAM	
  
Dr.	
  Jeremy	
  Bellucci	
  
Dr.	
  Christine	
  Wallace	
  
Elizabeth	
  Koeman	
  
Dr.	
  Peter	
  C.	
  Burns	
  
Nuclear	
  Forensics	
  
!   	
  As	
  “the	
  technical	
  means	
  by	
  which	
  nuclear	
  
materials,	
  whether	
  intercepted	
  intact	
  or	
  
retrieved	
  from	
  post-­‐explosion	
  debris,	
  are	
  
characterized	
  (as	
  to	
  composition,	
  physical	
  
condition,	
  age,	
  provenance,	
  history)	
  and	
  
interpreted	
  (as	
  to	
  provenance,	
  industrial	
  
history,	
  and	
  implications	
  for	
  nuclear	
  device	
  
design).”	
  Joint	
  Working	
  Group	
  of	
  the	
  American	
  Physical	
  Society	
  
and	
  the	
  American	
  Association	
  for	
  the	
  Advancement	
  of	
  Science	
  (2010)	
  
Questions	
  addressed	
  by	
  nuclear	
  forensic	
  
analysis	
  &	
  associated	
  time	
  frames	
  
!   What	
  the	
  event	
  a	
  nuclear	
  explosion?	
  
What	
  was	
  the	
  yield?	
  
!   Was	
  U	
  or	
  Pu	
  used?	
  or	
  both?	
  	
  
Level	
  of	
  sophistication	
  of	
  device?	
  
!   Isotopic	
  composition	
  of	
  fuel	
  components?	
  
Provenance	
  and	
  history?	
  
Do	
  isotope	
  compositions	
  of	
  debris	
  match	
  any	
  from	
  known	
  
weapon	
  tests?	
  
!   What	
  was	
  the	
  most	
  probable	
  design	
  of	
  the	
  device?	
  
Do	
  these	
  match	
  any	
  existing	
  designs?	
  
Any	
  other	
  materials	
  present	
  that	
  might	
  suggest	
  a	
  particular	
  
source? 	
   	
   	
   	
   	
   	
   	
  
	
   	
   	
  	
  
Hours	
  
Hours-­‐	
  
Days	
  
Days	
  
Several	
  
weeks	
  
Forensic	
  Analysis	
  
Post-­‐Detonation	
  Materials	
  (PDMs)	
  
Historic	
  Test	
  Sites	
  
	
  
!   Ideal	
  for	
  establishing	
  and	
  developing	
  nuclear	
  forensics	
  protocols	
  
since	
  the	
  chemical	
  and	
  isotopic	
  composition	
  of	
  weapons	
  
employed	
  are	
  well	
  documented;	
  PDMs	
  provide	
  a	
  means	
  to	
  
validate	
  forensic	
  results	
  
!   Once	
  these	
  new	
  forensic	
  techniques	
  have	
  been	
  established,	
  
these	
  can	
  be	
  applied	
  to	
  more	
  recent	
  and	
  sophisticated	
  nuclear	
  
detonations	
  
! Source	
  attribution	
  is	
  the	
  ultimate	
  goal	
  of	
  nuclear	
  forensics!!	
  
!   Trinity	
  Test	
  –	
  Detonation	
  of	
  First	
  Nuclear	
  
Device	
  
	
  
Why	
  is	
  the	
  study	
  of	
  post-­‐detonation	
  
materials	
  from	
  the	
  Trinity	
  test	
  a	
  good	
  
starting	
  point?	
  
	
  
!   Design	
  of	
  trinity	
  device	
  was	
  relatively	
  
“simple”	
  and	
  detonated	
  in	
  a	
  remote	
  
location	
  with	
  “simple”	
  geologic	
  
background	
  (i.e.,	
  desert	
  sand)	
  
	
  
http://www.trinityremembered.com/
photos/index.html	
  
TRINITY	
  TEST	
  
!   World’s	
  first	
  detonation	
  
of	
  a	
  nuclear	
  device	
  
!   Nicknamed	
  “Gadget”	
  
!   July	
  16,	
  1945	
  at	
  White	
  
Sands	
  Missile	
  Range,	
  NM	
  
!   Detonated	
  from	
  a	
  ~30	
  m	
  
high	
  tower	
  
!   239Pu-­‐implosion	
  device	
  
!   Equiv.	
  to	
  21	
  kilotons	
  of	
  
TNT	
  
http://www.trinityremembered.com/
photos/index.html	
  
www.awesomestories.com	
  
WHAT	
  IS	
  TRINITITE?	
  
•  The	
  explosion	
  resulted	
  in	
  the	
  
partial	
  melting	
  of	
  the	
  surrounding	
  
desert	
  sand	
  and	
  incorporated	
  
components	
  of	
  the	
  device	
  and	
  test	
  
site	
  materials,	
  which	
  subsequently	
  
fused	
  into	
  blast-­‐melt	
  glass	
  referred	
  
to	
  as	
  Trinitite.	
  
-­‐	
  Predominantly	
  composed	
  of	
  silica-­‐
rich	
  glass	
  
	
  
-­‐	
  Contains	
  remnant	
  mineral	
  grains	
  
from	
  desert	
  (arkosic	
  sand):	
  
Quartz,	
  Feldspars,	
  Micas,	
  Calcite,	
  
Gypsum,	
  minor	
  amounts	
  of	
  
ferromagnesian	
  minerals,	
  
zircons	
  
	
  
-­‐  Can	
  contain	
  remnants	
  of	
  the	
  
device,	
  tower,	
  diagnostic	
  
equipment:	
  mostly	
  copper	
  and	
  iron	
  
!   SITE	
  SELECTION:	
  
Flat	
  area	
  –	
  minimize	
  extraneous	
  
effect	
  of	
  the	
  blast;	
  
Good	
  weather	
  –	
  necessary	
  for	
  
good	
  optical	
  information;	
  
Minimum	
  20	
  km	
  distance	
  -­‐	
  from	
  
nearest	
  settlement;	
  
Proximity	
  to	
  Los	
  Alamos	
  –	
  
minimize	
  transportation	
  of	
  
personnel	
  and	
  materials;	
  
	
  
	
  
A=	
  Red	
  inclusions;	
  B=	
  Black	
  inclusions;	
  C=	
  “Coke	
  Bottle”;	
  D=	
  “Regular”,	
  green	
  trinitite	
  
Trinitite	
  Samples	
  
!   A	
  =	
  glass-­‐like	
  fused	
  surface;	
  B	
  =	
  large	
  gas	
  pockets	
  on	
  surface/perimeter	
  
C	
  =	
  rough	
  texture	
  of	
  desert	
  surface;	
  D	
  =	
  red	
  inclusions;	
  E	
  =	
  black	
  
inclusions;	
  F	
  =	
  light	
  colored	
  glass;	
  G	
  =	
  blue	
  inclusions;	
  H	
  =	
  white	
  
inclusions;	
  I	
  =	
  “Coke-­‐bottle”	
  inclusions;	
  J	
  =	
  light/dark	
  colored	
  layered	
  
glass;	
  K	
  =	
  protuberances/casts;	
  L	
  =	
  metallic-­‐like	
  coating;	
  M	
  =	
  elongated	
  
extrusions;	
  N	
  =	
  lace-­‐like	
  structures;	
  O	
  =	
  iron	
  inclusions	
  
	
  
Glass-­‐like	
  fused	
  
top	
  surface	
  
Bottom	
  side	
  shows	
  
rough	
  texture	
  of	
  
precursor	
  desert	
  
sand	
  
Vesicles	
  	
  	
  
“Multi-­‐scale	
  Separation	
  &	
  Analysis	
  of	
  
Heterogeneous	
  Trinitite	
  Phases”	
  
	
  !  GOALS	
  and	
  OBJECTIVES	
  
!   Conduct	
  detailed	
  chemical	
  and	
  isotopic	
  characterization	
  
of	
  trinitite	
  samples	
  at	
  high	
  spatial	
  resolution,	
  i.e.	
  micron	
  
scale	
  –	
  development	
  of	
  ‘forensic	
  tools’	
  
!   The	
  latter	
  will	
  be	
  accomplished	
  using	
  a	
  combination	
  of	
  
micro-­‐analytical	
  techniques	
  such	
  as	
  Electron	
  Microprobe	
  
Analysis	
  (EMPA),	
  Scanning	
  Electron	
  Microscopy	
  (SEM),	
  
Focused	
  Ion	
  Beam	
  (FIB),	
  Transmission	
  Electron	
  
Microscopy	
  (TEM),	
  and	
  Laser-­‐Ablation-­‐Inductively	
  
Coupled	
  Plasma	
  Mass	
  Spectrometry	
  (LA-­‐ICP-­‐MS).	
  
!   Development	
  of	
  scientific	
  expertise	
  in	
  the	
  area	
  of	
  
nuclear	
  forensics	
  for	
  graduate	
  students	
  and	
  
postdoctoral	
  researcher	
  involved.	
  
Analytical	
  Methods	
  
!   BULK	
  SAMPLE:	
  
	
   	
  -­‐	
  Opitcal	
  microscopy	
  
	
   	
  -­‐	
  Gamma	
  spectroscopy	
  
	
   	
  -­‐	
  Alpha	
  track	
  radiography	
  
	
   	
  -­‐	
  Beta	
  autoradiography	
  
	
   	
  -­‐	
  Micro-­‐	
  XRF	
  
	
   	
  -­‐	
  Laser	
  fluorination	
  (stable	
  oxygen	
  isotope)	
  
!   Micron-­‐scale:	
  
	
   	
  -­‐	
  SEM-­‐EDS	
  
	
   	
  -­‐	
  EMP	
  
	
   	
  -­‐	
  FIB/	
  TEM	
  
	
   	
  -­‐	
  LA-­‐(MC)-­‐ICP-­‐MS	
  
	
  
Origin	
  of	
  Radionuclides-­‐	
  
Gamma	
  Spectroscopy	
  
Bulk	
  Analysis	
  –	
  Gamma	
  Spectroscopy	
  
Bellucci	
  et	
  al.	
  (2013a,	
  JNRC)	
  
Bellucci	
  et	
  al.	
  (2013a,	
  JNRC)	
  
Bellucci	
  et	
  al.	
  (2013a,	
  JNRC)	
  
Bellucci	
  et	
  al.	
  (2013a,	
  JNRC)	
  
Bellucci	
  et	
  al.	
  (2013a,	
  JNRC)	
  
Gamma	
  Spectroscopy	
  –	
  
Conclusions	
  
!   	
  Based	
  on	
  the	
  relative	
  activities	
  of	
  137Cs,	
  155Eu,	
  
239Pu,	
  and	
  241Am,	
  a	
  similar	
  behavior	
  of	
  these	
  
isotopes	
  during	
  the	
  Trinity	
  test	
  is	
  observed.	
  
!   	
  The	
  behavior	
  of	
  133Ba	
  does	
  not	
  correlate	
  with	
  
any	
  of	
  the	
  bomb-­‐derived	
  isotopes,	
  and	
  
therefore,	
  its	
  exact	
  origin	
  remains	
  ambiguous.	
  
!   	
  Based	
  on	
  the	
  activity	
  of	
  152Eu,	
  a	
  spatial	
  model	
  
calculation	
  for	
  the	
  radioisotopes	
  indicates	
  their	
  
homogeneous	
  distribution.	
  
Bellucci	
  et	
  al.	
  (2013a,	
  JNRC)	
  
Detailed,	
  In-­‐situ	
  
Microanalysis	
  
SEM	
  Investigation	
  of	
  Inclusions	
  –	
  
Trinitite	
  Surfaces	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
TRINITITE-­‐HOSTED	
  INCLUSIONS	
  
Origin	
  –	
  desert	
  sand	
  
Origin	
  –	
  gadget	
  device	
  &	
  materials,	
  blast	
  tower,	
  	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
TRINITITE-­‐HOSTED	
  INCLUSIONS	
  
Fe-­‐Si	
  
Fe-­‐Si	
  
X-­‐ray	
  surface	
  map	
   BSE-­‐	
  chemistry	
  
TRINITITE-­‐HOSTED	
  INCLUSIONS	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
Pb	
  
X-­‐ray	
  surface	
  map	
   BSE-­‐	
  chemistry	
  
TRINITITE-­‐HOSTED	
  INCLUSIONS	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
Ba	
  
W-­‐Ta-­‐Ga	
  
X-­‐ray	
  surface	
  map	
   BSE-­‐	
  chemistry	
  
TRINITITE-­‐HOSTED	
  INCLUSIONS	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
Ti	
  
Fe-­‐Ti	
  
X-­‐ray	
  surface	
  map	
   BSE-­‐	
  chemistry	
  
Blast	
  modeling	
  –	
  Inclusion	
  work	
  
Two-­‐stage	
  process	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
Conclusions	
  –	
  	
  
Trinitite-­‐hosted	
  inclusions	
  
! RELIEF:	
  
	
  –	
  “Flat”	
  or	
  “Bell-­‐shaped”	
  inclusions	
  formed	
  
simultaneously	
  with	
  main	
  phase	
  of	
  blast	
  melt	
  
-­‐	
  “Topographic”	
  inclusions	
  precipitated	
  (“rained	
  
down”)	
  later	
  
	
  
! ORIGIN	
  of	
  ELEMENTS:	
  
-­‐	
  Fe-­‐Ti	
  –	
  blast	
  tower	
  
-­‐	
  Pb,	
  Ta,	
  W	
  –	
  tamper	
  of	
  device	
  
-­‐	
  Ga	
  –	
  alloyed	
  with	
  Pu	
  during	
  enrichment	
  process	
  
-­‐	
  Ba	
  –	
  device	
  +	
  natural	
  
Bellucci	
  &	
  Simonetti	
  (2012,	
  J.	
  Radioanalytical	
  Nuclear	
  Chemistry)	
  
Distribution	
  of	
  Radioactive	
  Elements-­‐	
  
Micron	
  scale	
  
Optical map
(PPL)
Alpha track
radiography
Beta
autoradiography
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Trinitite	
  
!   Composed	
  mostly	
  of	
  
relict	
  quartz	
  grains	
  
(dark)	
  and	
  trinitite	
  
“glass”	
  light	
  
!   Constrain	
  the	
  
composition	
  of	
  melt	
  
BSE	
  image	
  of	
  trinitite.	
  Courtesy	
  of	
  T.	
  Hainley	
  	
  BSE	
  image	
  of	
  trinitite.	
  Courtesy	
  of	
  T.	
  Hainley	
  	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Trace	
  Element	
  Analysis	
  
!   Laser	
  Ablation	
  ICP-­‐MS 	
  	
  
!   Parameters:	
  
!   Standard:	
  NIST	
  612	
  
!   Spot	
  Size:	
  55μm	
  
!   Frequency:	
  5	
  Hz	
  
! Fluence:	
  ~12	
  J/cm2	
  
!   New	
  Wave	
  Research	
  UP-­‐213	
  
Nd:YAG	
  laser	
  &	
  Element2	
  HR-­‐
ICP-­‐MS	
  
Midwest	
  Isotope	
  and	
  Trace	
  Element	
  
Research	
  Analytical	
  Center	
  (MITERAC)	
  
LA-­‐ICP-­‐MS	
  Analyses	
  -­‐	
  Radionuclides	
  	
  	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Pu/Zr	
  >0.014	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
240Pu/239Pu	
  =	
  0.0208	
  ±	
  0.0012	
  
235U/238U	
  =	
  0.00718	
  ±	
  0.00018	
  
Distribution	
  of	
  Radioactive	
  Elements	
  –	
  
Conclusions	
  
!   Demonstrate	
  for	
  the	
  first	
  time	
  that	
  device-­‐related	
  
radionuclides	
  (e.g.,	
  U,	
  Pu)	
  are	
  found	
  primarily	
  within	
  
the	
  melt	
  (glassy)	
  component	
  of	
  trinitite.	
  
!   	
  In	
  areas	
  characterized	
  by	
  higher	
  Pu	
  ion	
  signals	
  (i.e.,	
  
abundances),	
  these	
  also	
  contain	
  elevated	
  contents	
  of	
  
U	
  and	
  fission	
  products	
  (e.g.,	
  137Cs),	
  which	
  confirm	
  their	
  
association	
  with	
  the	
  device.	
  
!   	
  In	
  contrast,	
  crystalline	
  (relatively	
  intact,	
  precursor)	
  
mineral	
  phases,	
  such	
  as	
  quartz,	
  K-­‐feldspar,	
  are	
  
essentially	
  devoid	
  of	
  radionuclides	
  and	
  other	
  device-­‐
related	
  components.	
  
Wallace	
  et	
  al.	
  (2013,	
  JRNC)	
  	
  
Distribution	
  of	
  Major	
  &	
  Trace	
  Elements	
  
!   Can	
  the	
  distribution	
  of	
  major	
  and	
  trace	
  
element	
  abundances	
  for	
  Trinitite	
  
obtained	
  in-­‐situ	
  by	
  Electron	
  Microprobe	
  
&	
  LA-­‐ICP-­‐MS	
  be	
  used	
  to	
  decipher	
  
natural	
  vs.	
  anthropogenic	
  (device-­‐
related)	
  components?	
  
!   13	
  Trinitite	
  samples	
  were	
  investigated	
  –	
  
total	
  of	
  117	
  LA-­‐ICP-­‐MS	
  analyses	
  
FeO%
SiO2
%
MnO%
FeO%
2
NaO%
FeO%
Al2
O3
%
To Quartz
FeO%
MgO%
FeO%
TiO2
%
FeO%
To Quartz
K2
O%
CaO%
FeO%
Calcite
K-Feldspar
40
45
50
55
60
65
70
75
80
0 1 2 3 4 5 6 7 8
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0 1 2 3 4 5 6 7 8
0
0.5
1
1.5
2
2.5
3
3.5
0 1 2 3 4 5 6 7 8
FeO%
Anthropogenic?
Anthropogenic?
Anthropogenic?
To K-spar
To Calcite
To K-spar
To Quartz
To Calcite
To Plagioclase, Chlorite
To Quartz
0
5
10
15
20
25
0 1 2 3 4 5 6 7 8
0
0.5
1
1.5
2
2.5
3
3.5
0 1 2 3 4 5 6 7 8
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
0 1 2 3 4 5 6 7 8
0
2
4
6
8
10
12
14
16
18
0 1 2 3 4 5 6 7 8
1-3.59a
3-5.25b
4F 2.36a
4C-10.60a
4F 2.36
4D-9.18a
4e-5.22b
4b-2.64b
4a-1.95a
5D-1.72B
5B-10.4B
4F-5.37
5A-6.06
0
10
20
30
40
50
60
0 1 2 3 4 5 6 7 8
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
Trace	
  Elements	
  Patterns	
  
!   Normalize	
  to	
  
upper	
  
continental	
  
crust	
  	
  
!   Looking	
  for	
  
anomalous	
  
compositions	
  
!   Order	
  by	
  
condensation	
  
temperature	
  
<-­‐-­‐-­‐-­‐-­‐Highest	
  condensation	
  temperature	
  
Samples	
  with	
  no	
  clear	
  mineral	
  
enrichments	
  	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
Nb	
  and	
  Ta:	
  Enriched	
  
Anthropogenic	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
Nb	
  and	
  Ta:	
  Enriched	
  
Anthropogenic	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
Natural	
  Enrichments	
  
Zircon	
  
Apatite	
  
Monazite	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
U	
  enrichment	
  without	
  geologic	
  
indicators	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
Metals	
  define	
  linear	
  correlations	
  
Indicate	
  mixing	
  between	
  
sand	
  and	
  likely	
  materials	
  
from	
  the	
  bomb	
  tower	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
Pb	
  
Cu	
  
Koeman	
  et	
  al.	
  (in	
  prep.)	
  
Lead	
  Concentrations	
  (ppm)	
  
FOV	
  2.5mm	
  
8100	
   15,600	
  
12,500	
  
7000	
  
6900	
  
Origins	
  of	
  Trace	
  Elements	
  
!   Most	
  trace	
  elements	
  can	
  be	
  attributed	
  to	
  precursor	
  	
  
minerals	
  within	
  desert	
  sand:	
  
!   Calcite/Gypsum:	
  Sr	
  
!   Barite:	
  Ba	
  
!   K-­‐feldspar:	
  Cs,	
  Rb,	
  Ga	
  
! Ilmenite:	
  Nb,	
  Ta	
  
!   Apatite,	
  Monazite,	
  Zircon:	
  U,	
  Th,	
  Y,	
  Hf,	
  REEs	
  
!   Except	
  for	
  metals:	
  Nb,	
  Ta,	
  Cu,	
  Co,	
  Cr,	
  Pb	
  
!   	
  Some	
  U	
  is	
  not	
  from	
  natural	
  background	
  
Bellucci	
  et	
  al.	
  (in	
  press,	
  Chemical	
  Geology)	
  
U	
  &	
  Pb	
  isotope	
  compositions	
  of	
  Trinitite	
  
Bellucci	
  et	
  al.	
  (2013b,	
  Analytical	
  Chemistry)	
  
Uranium	
  isotopes	
  
!   238U	
  
!   236U:	
  Produced	
  by	
  neutron	
  capture	
  of	
  un-­‐
fissioned	
  235U	
  	
  and	
  decay	
  of	
  240Pu	
  
!   235U:	
  Produced	
  by	
  decay	
  of	
  239Pu	
  
!   234U:	
  Produced	
  by	
  decay	
  of	
  238Pu	
  
!   All	
  U	
  have	
  half-­‐lives	
  that	
  are	
  long	
  enough	
  to	
  
make	
  them	
  appear	
  stable	
  since	
  the	
  time	
  of	
  
detonation	
  
Bellucci	
  et	
  al.	
  (2013b,	
  Analytical	
  Chemistry)	
  
Pu-­‐Isotope	
  Systematics	
  
!   240Pu-­‐-­‐>236U	
  	
  
!   Half	
  life:	
  6,560	
  y	
  
!   239Pu-­‐-­‐>235U	
  
!   Half	
  life:	
  24,100	
  y	
  
!   238Pu-­‐-­‐>234U	
  
!   Half	
  life:	
  87.7	
  y	
  
Bellucci	
  et	
  al.	
  (2013b,	
  Analytical	
  Chemistry)	
  
Isotope	
  Analysis	
  
61	
  
Laser	
  Ablation	
  Multi	
  Collector	
  ICP-­‐MS	
  
!   Nu	
  Plasma	
  II	
  Parameters	
  
!   ESI	
  New	
  Wave	
  193	
  Excimer	
  
Uranium	
  isotopes	
  
Natural	
  U	
  in	
  tamper	
  
Natural	
  U	
  in	
  geology	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Uranium	
  isotopes	
  
Fission	
  changes	
  tamper	
  composition	
  
&	
  mixes	
  with	
  natural	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Uranium	
  Isotopes	
  
Least	
  diluted	
  tamper	
  isotopic	
  
composition	
  
Tamper	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Influence	
  of	
  Pu	
  
!   Assuming	
  an	
  initial	
  U	
  isotopic	
  
composition	
  
!   Known	
  half-­‐lives	
  
!   One	
  can	
  mathematically	
  predict	
  the	
  U	
  
isotopic	
  composition	
  resulting	
  from	
  
the	
  in-­‐growth	
  of	
  Pu	
  over	
  ~68	
  years	
  
!   235U/238U	
  (present)	
  =	
  235U/238U	
  (initial)	
  +	
  239Pu/238U	
  *	
  (eλ239Put	
  –1)	
  
!   236U/238U	
  (present)	
  =	
  236U/238U	
  (initial)	
  +	
  239Pu/238U	
  *240Pu/239Pu	
  *	
  
(eλ240Put	
  –1)	
  
!   234U/238U	
  (present)	
  =	
  234U/238U	
  (initial)	
  +	
  239Pu/238U	
  *238Pu/239Pu	
  *	
  
(eλ238Put	
  –1)	
  
Pu	
  model	
  of	
  “super	
  grade	
  Pu”	
  
Tamper	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Spots	
  with	
  high	
  Pu	
  
concentrations	
  
Tamper	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Pu-­‐model	
  
Tamper	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Spots	
  with	
  high	
  Pu	
  
concentrations	
  
Tamper	
  
Bellucci	
  et	
  al.	
  (2013b)	
  
Conclusions	
  
!   Forensic	
  investigation	
  of	
  PDMs	
  is	
  complex	
  and	
  
requires	
  a	
  multi-­‐analytical	
  approach	
  for	
  accurate	
  
assessment	
  of	
  device’s	
  chemical	
  &	
  isotopic	
  
composition	
  
!   Traditional	
  protocols	
  involving	
  “bulk”	
  samples	
  are	
  
time-­‐consuming	
  and	
  will	
  tend	
  to	
  “average	
  out”	
  the	
  
chemical	
  and	
  isotopic	
  signals	
  from	
  device	
  and	
  matrix	
  
components	
  
!   Micro-­‐analytical	
  approach	
  can	
  provide	
  both	
  rapid	
  and	
  
accurate	
  forensic	
  information	
  –	
  key	
  attributes	
  for	
  
source	
  attribution	
  purposes	
  
On-­‐going	
  Research	
  -­‐	
  Trinitite	
  
! Pu	
  isotope	
  analysis	
  –	
  LA-­‐MC-­‐ICP-­‐MS	
  (Dr.	
  S.	
  
Mana)	
  
!   Oxygen	
  isotope	
  analysis	
  –	
  laser	
  fluorination	
  (E.	
  
Koeman	
  et	
  al.,	
  in	
  press,	
  Analytical	
  Chemistry)	
  
! Pb	
  isotope	
  analysis	
  of	
  “Red	
  areas”	
  –	
  LA-­‐MC-­‐
ICP-­‐MS	
  (E.	
  Koeman	
  &	
  J.	
  Bellucci)	
  
!   Li	
  isotope	
  analysis	
  –	
  MC-­‐ICP-­‐MS	
  (T.	
  Magna,	
  
Czech	
  Geol.	
  Survey)	
  
Lead	
  Isotopes	
  in	
  Trinitite	
  
75	
  
36.50	
  
37.00	
  
37.50	
  
38.00	
  
38.50	
  
39.00	
  
39.50	
  
40.00	
  
16.50	
   17.00	
   17.50	
   18.00	
   18.50	
   19.00	
   19.50	
  
208Pb/204Pb	
  
206Pb/204Pb	
  
15.30	
  
15.40	
  
15.50	
  
15.60	
  
15.70	
  
15.80	
  
15.90	
  
16.50	
   17.00	
   17.50	
   18.00	
   18.50	
   19.00	
   19.50	
  
207Pb/204Pb	
  
206Pb/204Pb	
  
36.50	
  
37.00	
  
37.50	
  
38.00	
  
38.50	
  
39.00	
  
39.50	
  
40.00	
  
16.50	
   17.00	
   17.50	
   18.00	
   18.50	
   19.00	
   19.50	
  
208Pb/204Pb	
  
206Pb/204Pb	
  
Trini0te	
  Glass	
  
Red	
  Area	
  
15.30	
  
15.40	
  
15.50	
  
15.60	
  
15.70	
  
15.80	
  
15.90	
  
16.50	
   17.00	
   17.50	
   18.00	
   18.50	
   19.00	
   19.50	
  
207Pb/204Pb	
   206Pb/204Pb	
  
Trini0te	
  Glass	
  
Red	
  Area	
  
Koeman	
  et	
  al.	
  (in	
  prep.)	
  
Pb	
  Isotopes	
  
77	
  
Estimated	
  Device	
  Composition	
  
36.50	
  
37.00	
  
37.50	
  
38.00	
  
38.50	
  
39.00	
  
39.50	
  
40.00	
  
16.50	
   17.00	
   17.50	
   18.00	
   18.50	
   19.00	
   19.50	
  
208Pb/204Pb	
  
206Pb/204Pb	
  
Trini0te	
  Glass	
  
Red	
  Area	
  
15.30	
  
15.40	
  
15.50	
  
15.60	
  
15.70	
  
15.80	
  
15.90	
  
16.50	
   17.00	
   17.50	
   18.00	
   18.50	
   19.00	
   19.50	
  
207Pb/204Pb	
   206Pb/204Pb	
  
Trini0te	
  Glass	
  
Red	
  Area	
  
Est.	
  Device	
  
Comp.	
   Est.	
  Device	
  
Comp.	
  
Koeman	
  et	
  al.	
  (in	
  prep.)	
  
! Buchans	
  Mine,	
  NFLD	
  (Canada)	
  
!   Only	
  mine	
  active	
  	
  
!   Mined	
  by	
  American	
  Smelting	
  
and	
  Refining	
  Co.	
  from	
  
1928-­‐1984