RECONSTRUCTING THE PAST, UNDERSTANDING THE PRESENT
AND PREDICTING THE FUTURE BASED ON
ISOTOPIC ANALYSIS VIA
MULTI-COLLECTOR ICP - MASS SPECTROMETRY
Frank Vanhaecke
Ghent University, Belgium
ICP – MASS SPECTROMETRY
 Analytical technique for (ultra)trace element analysis
►° 1983
 Compared to AAS
►Even lower LODs
►Multi-element capabilities
 Compared to ICP-OES
►Lower LODs
ICP – MASS SPECTROMETRY
 Analytical technique for (ultra)trace element analysis
►° 1983
 Compared to AAS
►Even lower LODs
►Multi-element capabilities
 Compared to ICP-OES
►Lower LODs
 Compared to AAS & ICPOES
►Isotopic information !!
99ISOTOPES ?
 Isotopes of an element M:
► same atomic number A
• Same number of protons in their nuclei
• Same number of electrons in their shells
 Identical chemical behaviour
• First approximation – statement will be refined later on
► Different mass number Z
• Different number of neutrons in their nuclei
 Different masses
 Notation
• or
 Terminology?
► Isotope: same place in PSE
► Todd & Soddy (early 20th century)
XA
Z XA
DISCOVERY OF ISOTOPES
 Separation of isotopes according to their mass in MS
► Thomson: separation of Ne+ isotopes in magnetic field
► Later on: Aston → isotopes for a suite of elements
http://www.hibbing.edu/chem/abomb/page_id_64208.html
ISOTOPES ?
 Mono-isotopic elements?
► 9Be, 19F, 23Na, 27Al, 31P, 45Sc, 55Mn, 59Co, 75As, 89Y, 93Nb, 103Rh, 127I,
133Cs, 141Pr, 159Tb, 165Ho, 169Tm, 197Au, 209Bi, 231Pa, 232Th
 Other elements?
► 2 – 10 isotopes
THE ISOTOPIC COMPOSITION OF THE ELEMENTS
 First approximation:
all elements show an isotopic composition that is stable in nature
 Why ?
► Thorough mixing during formation of our solar system (4.6 . 109 years BP)
The solar system was formed approximately 4.5 billion
years ago. The material making up the solar system all
came from a single, mostly homogeneous cloud of
material (solar nebula). The matter rotated in a flattened
plane, splayed out in a disk due to the angular
momentum. With time, material not falling to the central
sun, would either be thrown out of the system or begin to
collect and build up planetesimals. At safe relative
distances, planetesimals built up to form the planets.
THE ISOTOPIC COMPOSITION OF THE ELEMENTS
1. Decay of naturally occurring, long-lived radionuclides
2. Natural isotope fractionation effects
3. Man-made variations
4. Interaction of cosmic rays with terrestrial matter
5. Variations observed in extra-terrestrial materials
THE ISOTOPIC COMPOSITION OF THE ELEMENTS
1. Decay of naturally occurring, long-lived radionuclides
2. Natural isotope fractionation effects
3. Man-made variations
4. Interaction of cosmic rays with terrestrial matter
5. Variations observed in extra-terrestrial materials
THE ISOTOPIC COMPOSITION OF THE ELEMENTS
 Importance of isotope ratio precision?
1. Decay of naturally occurring, long-lived radionuclides
2. Natural isotope fractionation effects
3. Man-made variations
4. Interaction of cosmic rays with terrestrial matter
5. Variations observed in extra-terrestrial materials
Isotoperatio
? 2 different populations  conclusions!
MULTI-COLLECTOR ICP – MASS SPECTROMETRY
Isotope ratio precision:
down to 0,002 % RSD !
MULTI-COLLECTOR ICP – MASS SPECTROMETRY
INSTRUMENTAL MASS DISCRIMINATION
► Caused by space-charge effects
► Preferential transmission of the heavier isotope
► Afftected by
• Matrix composition
• Target element concentration
 Mass discrimination
► Measured ratio  true value
► Order of magnitude
• ca. 1% per mass unit @ mid-mass
• Considerably larger @ low masses
► Not a systematic f(time)
Isolation
of target element
required
CHROMATOGRAPHIC ISOLATION OF TARGET ELEMENT
 Class-10 clean lab facilities
< 10 particles / ft3 @ 0.5 µm vs. millions particles / ft3
Ultrapure water & acids
Discipline!
LECTURE CONTENT ?
 Real-life applications
► Ghent University & international literature
MEASURING NATURAL VARIATION
ELEMENTS WITH RADIOGENIC ISOTOPES
Sr isotope Natural range of
relative isotopic abundance
84
Sr 0.55 – 0.58 %
86
Sr 9.75 – 9.99 %
87
Sr 6.94 – 7.14 %
88
Sr 82.29 – 82.75 %
IUPAC, 1997
Pb isotope Natural range of
relative isotopic abundance
204
Pb 1.04 – 1.65 %
206
Pb 20.84 – 27.48 %
207
Pb 17.62 – 23.65 %
208
Pb 51.28 – 56.21 %
IUPAC, 1997
87Rb → 87Sr + β- + ν
238U → 206Pb, 235U → 207Pb, 232Th → 208Pb
NATURAL VARIATIONS IN
THE ISOTOPIC COMPOSITION OF PB
► 238U  206Pb
► 235U  207Pb
► 232Th  208Pb
► 204Pb: not radiogenic
NATURAL VARIATIONS IN
THE ISOTOPIC COMPOSITION OF PB
 Pronounced variation
 Pb in the earth’s crust
► Shows isotopic variation, but 206Pb/207Pb ~ 1.20
 Pb in ores
► Shows isotopic variation, but << 1.20
• Separated from Th & U @ time of ore formation
PbS ore – galena
Pb isotope Natural range of
relative isotopic abundance
204
Pb 1.04 – 1.65 %
206
Pb 20.84 – 27.48 %
207
Pb 17.62 – 23.65 %
208
Pb 51.28 – 56.21 %
IUPAC, 1997Böhlke et al., J. Phys. Ref. Data, 2005
PROVENANCE DETERMINATION OF
GLAZED TILES FROM A MEDIAEVAL CASTLE
USING PB ISOTOPIC ANALYSIS
PIETER BLADELIN
 Pieter Bladelin
►Governor general of all finances of Philip the Good
• Duke of Burgundy & Count of Flanders
• Built a castle in 1448
his
castle
Pieter
Bladelin
Painting by Rogier van der Weyden
CASTLE OF MIDDELBURG
NEAR TO BRUGES (BELGIUM)
CASTLE OF MIDDELBURG
NEAR TO BRUGES (BELGIUM)
CASTLE OF MIDDELBURG
NEAR TO BRUGES (BELGIUM)
TILES FROM CASTLE OF MIDDELBURG
NEAR TO BRUGES (BELGIUM)
 Sn-glazed tiles
►PB  Pieter Bladelin
►Completely different from 15th century local & regional tiles
• Calcareous instead of siliceous & iron-rich
• Tin/lead glaze instead of salt or copper glaze
• Diring technology
►Resemblance to Valencian (Spain) tiles?
• Floral & islamic designs
ISOTOPIC ANALYSIS OF PB IN GLAZE
 Sample preparation
► Extraction of Pb out of glaze using acetic acid
► Isolation of Pb using extraction chromatography
► Apporpriate dilution & addition of Tl
• Internal standard for correction for mass discrimination
 Isotopic analysis
► Neptune MC-ICP-MS unit
 Data handling
► Correction for mass discrimination via Tl
► Exponential law
PbSPECTM
(Eichrom Technologies)
3-ISOTOPE PLOT FOR LEAD
37,5000
38,0000
38,5000
39,0000
39,5000
40,0000
15,4000 15,5000 15,6000 15,7000 15,8000 15,9000 16,0000 16,1000
208/204
207/204
Castle
3-ISOTOPE PLOT FOR LEAD
37,5000
38,0000
38,5000
39,0000
39,5000
40,0000
15,4000 15,5000 15,6000 15,7000 15,8000 15,9000 16,0000 16,1000
208/204
207/204
Castle Valencia
Castle of Alfonso V
- Room 1
Castle of Alfonso V
- Room 2
3-ISOTOPE PLOT FOR LEAD
37,5000
38,0000
38,5000
39,0000
39,5000
40,0000
15,4000 15,5000 15,6000 15,7000 15,8000 15,9000 16,0000 16,1000
208/204
207/204
Castle
Valencia
Spanish ores
3-ISOTOPE PLOT FOR LEAD
208PB/206PB VS. 207PB/206PB
 Valencia, Spain – castle of Alfonso V
 Middelburg, Belgium – castle of Pieter Bladelin
TILES FROM MIDDELBURG CASTLE
ARCHAEOMETRIC INVESTIGATION – CONCLUSIONS
 Next to Pb isotopic analysis:
► LA-ICP-MS
► XRF
► Raman spectroscopy
► Thin sections for petrographical assessment
 All results: tiles from
► Middelburg castle
► Castle of Alfonso V (Valencia)
common technological
context & common origin
TILES FROM MIDDELBURG CASTLE
ARCHAEOLOGICAL CONCLUSION
 Historic sources
► Strong socio-economical and cultural contacts between Philip the
Good and Alfonso V between 1444 and 1451
► “Presents” were a well-known practice in the context of 15th century
European elites
PROVENANCE DETERMINATION OF
SKELETAL REMAINS
USING SR ISOTOPIC ANALYSIS
VARIATIONS IN THE ISOTOPIC COMPOSITION OF SR
 Variations in Sr isotopic composition due to:
► 87Rb = naturally occurring, long-lived radionuclide
• T1/2 = 48.8 x 109 y
• Isotopic composition of Rb has changed through time
• Isotopic composition of Rb presently equal for all terrestrial materials
► Isotopic composition of Sr: variable!
• E.g., rocks: dependent on elemental Rb/Sr ratio + age
 SrRb 8787
Sr isotope Natural range of
relative
isotopic abundances
84Sr
86Sr
87Sr
88Sr
0.55 – 0.58%
9.75 – 9.99%
6.94 – 7.14%
82.29 – 82.75%
Böhlke et al., J. Phys. Ref. Data, 2005
PROVENANCE DETERMINATION
VIA SR ISOTOPIC ANALYSIS
 Varying geology
 Varying Sr isotopic composition
Flanders
Wallonia
Ardennes
50 km
Holocene
Pleistocene
Pliocene
Miocene
Oligocene
Eocene
Cretaceous
Jurassic
Triassic
Permian
upper-Carboniferous
lower-Carboniferous
Devonian
Silurian
Cambrian
Quaternary
Tertiary
Mesozoic
Palaeozoic
NATURAL VARIATIONS IN THE ISOTOPIC COMPOSITION OF SR –
PROVENANCE DETERMINATION OF AGRICULTURAL PRODUCTS
Transfer of Sr without
measurable isotopic
fractionation
NATURAL VARIATIONS IN THE ISOTOPIC COMPOSITION OF SR –
PROVENANCE DETERMINATION OF AGRICULTURAL PRODUCTS
 Provenancing agricultural products ?
► To detect incorrect indication of geographical origin (fraud)
 Which products?
► Of plant origin:
• Wine: Almeida & Vasconselos, JAAS, 2001, Barbaste et al., JAAS, 2002
• Cider: Garcia-Ruiz et al., ACA, 2007
• Rice: Kawasaki et al., Soil Sci Plant Nutr, 2002
• Ginseng: Choi et al., Food Chem, 2008
• Asparagus: Swoboda et al.,ABC, 2008
• …
► Of animal origin:
• Cheese: Fortunato et al., JAAS, 2004
• Caviar: Rodushkin et al., ACA, 2008
• …
AUTHENTICATION OF KALIX (NE SWEDEN) VENDACE CAVIAR
RODUSHKIN ET AL., ACA, 583, 310, 2007
87Sr/86Sr:
seasonal variation Kalix
< geographical variation
complemented with:
trace element fingerprint
Os isotopic analysis
SR ISOTOPIC ANALYSIS FOR
PROVENANCE DETERMINATION
Transfer of Sr without
measurable isotopic
fractionation
SR ISOTOPIC ANALYSIS FOR
PROVENANCE DETERMINATION OF HUMAN REMAINS
 Enamel
► Formed during early childhood
► 87Sr/86Sr ~ food age 1 – 7
 Dentine
► Continuously renewed
► Faster Sr turnover rate
► 87Sr/86Sr ~ food last years
 Useful info
► Archaeology
SR ISOTOPIC ANALYSIS FOR
PROVENANCE DETERMINATION OF HUMAN REMAINS
 St-Servatius basilica
► Maastricht, Netherlands
► 1600 years of history
► Early christianity in the Maas valley
► Important archaeological excavations
► Analysis of the grave-field population
• Locals and/or immigrants?
 Sr isotopic analysis of tooth tissue & soil (UGent & ETH)
► Acid digestion of samples (open beaker – HNO3 & HCl)
► Isolation of Sr using Sr-spec (Eichrom Technologies)
► Sr isotopic analysis using multi-collector ICP-MS
• Internal correction, based on constant 86Sr/88Sr
• Russell’s equation
SR ISOTOPIC ANALYSIS FOR
PROVENANCE DETERMINATION OF HUMAN REMAINS
87
Sr /
86
Sr enameldentine
0,7098
0,7090
0,7100
0,7092
0,7102
0,7094
0,7104
0,7096
0,7106
108-I
108-M
454-I
454-M
71-M
Pandhof population
I: incisor, M: molar
STILL VALID IN A GLOBAL WORLD ?
FROM A GAME TO A REAL-LIFE APPLICATION:
FORENSICS
 Case A: infant killed a few days after birth
► 87Sr/86Sr: if Belgium  coastal region
► Police enquiry
•  mother not natively living in that region?
• Lived mostly in that region during pregnancy
Flanders
Wallonia
Ardennes
50 km
Holocene
Pleistocene
Pliocene
Miocene
Oligocene
Eocene
Cretaceous
Jurassic
Triassic
Permian
upper-Carboniferous
lower-Carboniferous
Devonian
Silurian
Cambrian
Quaternary
Tertiary
Mesozoic
Palaeozoic
Degryse et al;, Anal Meth,
4, 2674-2679, 2012
FROM A GAME TO A REAL-LIFE APPLICATION:
FORENSICS
 Case B
► 87Sr/86Sr: if Belgium  coastal region
► No match with missing person from that area
► Search in other European areas with similar 87Sr/86Sr
► Possible match found  assumed origin confirmed later
 Case C
► 87Sr/86Sr: difference between bone & teeth (enamel)
• Bone: 87Sr/86Sr; if in Belgium  central Flanders
• Enamel 87Sr/86Sr: outside Benelux
► Police enquiry
• Victim came from outside Europe & lived for > 10 years in central Flanders
Degryse et al;, Anal Meth, 4, 2674-2679, 2012
GOING BACK FURTHER IN TIME …
Formation of
(our) solar system
THE 182HF-182W CHRONOMETER
S.B. JACOBSEN, EPSL, 33, 531, 2005
Very short compared to
age of solar system
Extinct
radionuclide
c
W isotopic analysis
TIMS: hampered by hihgh IE(W) = 7,98 eV
Straightforward with MC-ICPMS
c
THE 182HF-182W CHRONOMETER
S.B. JACOBSEN, EPSL, 33, 531, 2005
 Formation of a planet ?
► Accretion
• Growth of an object by attracting more matter (gravity)
► Differentiation
• Core formation
Iron core (heavy)
Crust (light)
Hf = lithophile

prefers crust
W = siderophile

prefers core
THE 182HF-182W CHRONOMETER
S.B. JACOBSEN, EPSL, 33, 531, 2005
 Effect of planetary differentiation?
► Situation 1: Hf & W only separated after extinction of 182Hf
• Hf/W ratio ~ chondritic meteorites (unfractionated reservoir)
► Situation 2: Hf & W were separated while 182Hf was still around
• High Hf/W ratio in crust  higher enrichment in 182W
 182Hf-182W chronometer
► Timing of planetary differentiation
THE 182HF-182W CHRONOMETER
S.B. JACOBSEN, EPSL, 33, 531, 2005
Increase in
182W/183W
In silicate fraction
MEASURING NATURAL VARIATION
ISOTOPE FRACTIONATION EFFECTS
 Different isotopes of an element
► Chemically identical
• Determined by number of electrons / protons
► Different mass
• Different efficiency in participation to
– Chemical reactions
– Physical processes
 Magnitude of isotope fractionation?
► Degree of participation to processes & reactions
► Relative mass difference between isotopes
• More pronounced for lighter elements
– H, C, N, O, S  IRMS
– Li, B
– All elements !
► Thermodynamics & kinetics
VARIATIONS IN ISOTOPIC COMPOSITION
NATURAL FRACTIONATION EFFECTS
 Very small effects
► Special notation introduced
  000,1
O
O
O
O
O
O
00
0O
dardtans
16
18
dardtans
16
18
sample
16
18
18




















H2O(gas) → isotopically lighterH2O(gas) → isotopically lighter
H2O(liq) → isotopically heavier
11B/10B AS A PALEO PH SEAWATER PROXY
 B in seawater:
► Present as B(OH)3 & B(OH)4
- / distribution dependent on pH
► 11B/10B isotope ratio in the past?  foraminifera & corals
pH pH
Concentration (µmol/kg) 11B
seawater
11B/10B AS A PALEO PH SEAWATER PROXY
 In seawater:
B(OH)3 + H2O  B(OH)4
- + H+
isotopically
heavier
isotopically
lighter
B(OH)4
- taken up
without isotopic fractionation
in corals & foraminifera
Foraminifera
living or fossil
eukaryotic monocellular
organisms with CaCO3 skeleton
pH of seawater as a
function(time)
RELEVANCE OF PH OF SEAWATER ?
 Determined by CO2 concentration in the atmosphere
► Information on CO2 level over geological times
► Is the current increase in CO2 level exceptional ?
CO2
H2CO3
RELEVANCE OF PH OF SEAWATER ?
?
OTHER ISOTOPE RATIOS AS PALEOPROXIES ?
 Paleoredox proxies: oxic/anoxic conditions in seawater
► Mo
► U
 Paleotemperature proxy: seawater
► Ca
 Paleoproxy for p(CO2)
► Si
e.g., marine sediments
e.g., bivalves
e.g., diatoms
S ISOTOPIC ANALYSIS FOR TRACING DOWN COUNTERFEIT DRUGS
R. CLOUGH ET AL., ANAL. CHEM., 78, 6126, 2006.
 Counterfeit drugs
► violation of intellectual property laws
► inappropriate quantities of active ingredients
► may contain ingredients that are not on the label (purity)
► often inaccurate, incorrect or fake packaging & labeling
 “Money making” drugs
S ISOTOPIC ANALYSIS FOR TRACING DOWN COUNTERFEIT DRUGS
R. CLOUGH ET AL., ANAL. CHEM., 78, 6126, 2006.
 S isotopic analysis in viagra using MC-ICP-MS
WHAT ABOUT THE FUTURE?
NATURAL ISOTOPE RATIO VARIATIONS IN A BIOMEDICAL CONTEXT
PIONEERING WORK – VON BLANCKENBURG & WALCZYK
Walczyk and von Blanckenburg, Science, 295, 2065 (2002)
NATURAL ISOTOPE RATIO VARIATIONS IN A BIOMEDICAL CONTEXT
PIONEERING WORK – VON BLANCKENBURG & WALCZYK
NATURAL ISOTOPE RATIO VARIATIONS IN A BIOMEDICAL CONTEXT
RESEARCH PROJECT @ GHENT UNIVERSITY
 Other diseases affecting the metabolism of essential elements
 change in isotopic composition in blood ?
 Our study
►Fe, Cu & Zn
►Step 1: spread in the reference population
• Determining factors ?
REMOVAL OF MATRIX ELEMENTS
SERONORM TRACE ELEMENTS WHOLE BLOOD
Na
Rb
Ba
Pb
Mg
P
S
Fe
Cu
Zn
K
0
2000000
4000000
6000000
8000000
10000000
12000000
14000000
Zn
Fe
Cu
m15
m14
m13
m12
m11
m10
m09
m08
m07
m06
m05
m04
m03
m02
m01
sl Na
Rb
Ba
Pb
Mg
P
S
Fe
Cu
Zn
K
Signalintensity(cps)
Van Heghe et al., JAAS, 27, 1327-1334, 2012
ISOLATION OF CU, FE & ZN
SERONORM TRACE ELEMENTS WHOLE BLOOD
0
20
40
60
80
100
Cu1
Cu2
Cu3
Cu4
Cu5
Cu6
Cu7
Cu8
Cu9
Cu10
Cu11
Cu12
Fe1
Fe2
Fe3
Fe4
Fe5
Fe6
Fe7
Fe8
Fe9
Fe10
Zn1
Zn2
Zn3
Zn4
Zn5
Zn6
Zn7
Zn8
Zn9
Zn10
Cu
Fe
Zn
Recovery(%)
100 % target element recovery  no effect of potential on-column fractionation
Van Heghe et al., JAAS, 27, 1327-1334, 2012
RESULTS FE ISOTOPIC ANALYSIS
HUMAN BLOOD / REFERENCE POPULATION
-4,6
-4,4
-4,2
-4,0
-3,8
-3,6
-3,4
-3,2
-3,0
-3,5 -3,0 -2,5 -2,0 -1,5
δ57Fe
δ56FeVegetarian Female
Vegetarian Male
Omnivorous Female
Omnivorous Male
MD correction based on Ni as int. std.
Van Heghe et al., JAAS, 27, 1327-1334, 2012
RESULTS ZN ISOTOPIC ANALYSIS
HUMAN BLOOD / REFERENCE POPULATION
-0,1
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4
δ67Zn
δ66Zn
Vegetarian Females
Vegetarian mailes
Omnivorous Females
Omnivorous Males
MD correction based on Cu as int. std.
Van Heghe et al., JAAS, 27, 1327-1334, 2012
RESULTS CU ISOTOPIC ANALYSIS
HUMAN BLOOD / REFERENCE POPULATION
-1 -0,8 -0,6 -0,4 -0,2 0 0,2 0,4 0,6
δ65Cu
Vegetarian Females
Vegetarian Males
Omnivorous Females
Omnivorous Males MD correction based on Zn as int. std.
?
Van Heghe et al., JAAS, 27, 1327-1334, 2012
RESULTS FE + ZN ISOTOPIC ANALYSIS
HUMAN BLOOD / REFERENCE POPULATION
-3,5
-3,0
-2,5
-2,0
-1,5
0 0,2 0,4 0,6 0,8
δ56Fe
δ67Zn
Vegetarian Female
Vegetarian Males
Omnivorous Females
Omnivorous Males
omnivorous vegetarian
Van Heghe et al., JAAS, 27, 1327-1334, 2012
FE, CU, ZN ISOTOPIC ANALYSIS IN HUMAN BLOOD
 Factors affecting isotope ratios in reference population
► Gender
► Feeding habits
► …
 Comparison Reference population vs. patient groups
► Diseases affecting Fe, Cu and/or Zn metabolism
► Diagnostic means?
• Less invasive
• Earlier stage of disease  prediction
 Use in archaeology?
ISOTOPIC ANALYSIS USING MC-ICP-MS
CONCLUSIONS
 Determining (geographical) provenance
 Unraveling history
 Solving crimes
 Diagnosing diseases
ISOTOPIC ANALYSIS USING MC-ICP-MS
CONCLUSIONS
 Determining (geographical) provenance
 Unraveling history
 Solving crimes
 Diagnosing diseases
 But be careful !
ISOTOPIC ANALYSIS USING MC-ICP-MS
CONCLUSIONS
 Determining (geographical) provenance
 Unraveling history
 Solving crimes
 Diagnosing diseases
 But be careful !