Inductively Coupled Plasma Inductively Coupled Plasma –– Mass Spectrometry (ICP-MS) Mass Spectrometry (ICP-MS)With or Without Laser Ablation (LA):With or Without Laser Ablation (LA):
For a Better UnderstandingFor a Better Understandingof Museum Collectionsof Museum Collections
Laure Dussubieux Laure Dussubieux –– Post-Doctoral Fellow Post-Doctoral Fellow
Smithsonian Centerfor Materials Research and Education
Inductively Coupled Plasma Inductively Coupled Plasma –– Mass Spectrometry Mass SpectrometryWith or Without Laser AblationWith or Without Laser Ablation
_ Multi-elemental analyticalmethod
_ Very low limits of detection: - in the range of ppm orbelow for solid sample - in the range of ppb orbelow for solution sample Inductively Coupled Plasma
LA-ICP-MSLA-ICP-MS
Ar
Ar
sample cell
sample
Laser Nd:YAG
266 nm
laser ablation
loadcoil
torch
cones
inductivelycoupled plasma
interface
vacuum pumps
quadrupole
lens
mass spectrometer
detector
signal conversion,ICP-MS and ablation
control L = 10.3 cm
l = 7.8 cm
H = 5.7 cm
Dimensions of the sample cell
Glass bead after analysis 100 micron ablation crater pit
The damage on the glass bead is quasi-invisible to the naked-eye.
Laser Ablation on glassLaser Ablation on glass
Gold coin after analysis 100 micron ablation crater pit
Laser Ablation on goldLaser Ablation on gold
The damage on the gold coin is quasi-invisible to the naked-eye.
Ar sample cell
sample
Laser Nd:YAG
266 nm
laser ablation
loadcoil
torch
cones
interface
vacuum pumps
quadrupole
lens
mass spectrometer
detector
signal conversion,ICP-MS and ablation
control
LA-ICP-MSLA-ICP-MS
Ar
inductivelycoupled plasma
Elements measurable with LA-ICP-MS or ICP-MSElements measurable with LA-ICP-MS or ICP-MS
Elements not measurable
Ar sample cell
sample
Laser Nd:YAG
266 nm
laser ablation
loadcoil
torch
cones
interface
vacuum pumps
quadrupole
lens
mass spectrometer
detector
signal conversion,ICP-MS and ablation
control
LA-ICP-MSLA-ICP-MS
Ar
inductivelycoupled plasma
Ar sample cell
sample
Laser Nd:YAG
266 nm
laser ablation
loadcoil
torch
cones
interface
vacuum pumps
quadrupole
lens
mass spectrometer
detector
signal conversion,ICP-MS and ablation
control
Ar
LA-ICP-MSLA-ICP-MS
inductivelycoupled plasma
Ar sample cell
sample
Laser Nd:YAG
266 nm
laser ablation
loadcoil
torch
cones
interface
vacuum pumps
quadrupole
lens
mass spectrometer
detector
signal conversion,ICP-MS and ablation
control
Ar
LA-ICP-MSLA-ICP-MS
inductivelycoupled plasma
Ar sample cell
sample
Laser Nd:YAG
266 nm
laser ablation
loadcoil
torch
cones
interface
vacuum pumps
quadrupole
lens
mass spectrometer
detector
signal conversion,ICP-MS and ablation
control
Ar
LA-ICP-MSLA-ICP-MS
inductivelycoupled plasma
Ar sample cell
sample
Laser Nd:YAG
266 nm
laser ablation
loadcoil
torch
cones
interface
vacuum pumps
quadrupole
lens
mass spectrometer
detector
signal conversion,ICP-MS and ablation
control
Ar
LA-ICP-MSLA-ICP-MS
inductivelycoupled plasma
Ar sample cell
Laser Nd:YAG
266 nm
loadcoil
torch
cones
interface
quadrupole
lens
mass spectrometer
detector
signal conversion
ICP-MSICP-MS
Ar
inductivelycoupled plasma
vacuum pumps
samplesolution
solutionintroduction
system
drain
Ar
spray chamberand nebulizer
_ Inorganic materials
_ Organic materials
Characterization of different materialsCharacterization of different materialswith ICP-MS or LA-ICP-MSwith ICP-MS or LA-ICP-MS
Siliceous materials
_ glass
_ glaze
Metals
_ gold alloy
_ copper alloy
Determination of the composition of inorganic materialsDetermination of the composition of inorganic materialsusing LA-ICP-MSusing LA-ICP-MS
Early 1600 to 1830 Blue Glass Trade Beads from NorthAmerica (Bill Billeck, Repatriation Office, NMNH).
_ Is there a variation of the composition according to thetime period ?
GLASSGLASS
19th century European and Asian Glass Trade Beads fromNorth America (Laurie Burgess, Repatriation Office, NMNH).
_ Characterization of the glass beads according to theirprovenance.
Ancient glass beads found inIndonesia (Bead Museum,Washington, DC).
_ What is the provenance of theglass used to manufacturedIndonesian beads ?
GLASSGLASS
From Ingredients to CompositionFrom Ingredients to Composition
Silica source Flux Coloring oropacifying agents
_ Sand
_ Quartz pebbles orcrushed siliceous stones
Si, Al, Fe, Ti, Ca, K, Mg,trace elements, rareearth, …
_ Plant ashes
_ Alkaline mineral deposit
_ Lead
Na, K, Pb, Ca, Mg, Cl, P,trace elements,…
_ Oxides
_ Metallic salts
Transition elements, Sb,Sn, Pb, Ca, traceelements
Orange – Indonesian beads fromthe Bead Museum
Grey – glass from South andSoutheast Asia, 2001
Potash flux
Mixed soda andpotash flux
Soda flux fromplant ashes
Soda flux frommineral deposits
MgO MgO + K+ K22O O –– Na Na22O O –– CaO CaO Ternary diagramTernary diagramfor the Different Fluxes Identifiedfor the Different Fluxes Identified
among Glass from South and Southeast Asiaamong Glass from South and Southeast Asia
0%
2%
4%
6%
8%
10%
12%
0% 2% 4% 6% 8% 10% 12% 14% 16%
Al2O3
CaO
AlAl22OO33 –– CaO CaO GraphGraphfor Glass from South and Southeast Asiafor Glass from South and Southeast Asia
High aluminaglass with sodaflux taken frommineral deposits
High calcium glasswith soda flux fromplant ashes
Orange – Indonesianbeads from the BeadMuseumGrey – glass from Southand Southeast Asia, 2001
Intermediatecomposition
0%
2%
4%
6%
8%
10%
12%
0% 2% 4% 6% 8% 10% 12% 14% 16%
Al2O3
CaO
AlAl22OO33 –– CaO CaO GraphGraphfor Glass from South and Southeast Asiafor Glass from South and Southeast Asia
921
927brownish
core
C
High calcium glasswith soda flux fromplant ashes
High alumina glasswith soda flux taken
from mineral deposits
Comparison between the composition of C and aComparison between the composition of C and aComposition Calculated as if 921 and 927 wereComposition Calculated as if 921 and 927 were
Mixed in Equal ProportionMixed in Equal Proportion
y = 1.0063x
R2 = 0.9992
0.10%
1.00%
10.00%
100.00%
0.1% 1.0% 10.0% 100.0%
1/2 (921) + 1/2 (927)
C =
933
P2O5
Cl
Fe2O3
K2OMgO
CaOAl2O3
Na2OSiO2
High alumina glasswith soda flux taken
from mineral deposits
High calcium glasswith soda flux fromplant ashes
921db
931db
931w
920g
914a_db
914a_w
933b
933y
933r
927tb
927yi
927ye
914b_w
914b_b
928_b
Imported glass(Middle-East)
Imported glass(South Asia)
C = Mixed glass
The Three Different Types of GlassThe Three Different Types of Glass
High calciumglass with sodaflux from plant
ashes
From Middle-East
High aluminaglass with sodaflux taken from
mineral deposits
From South Asia
Mixed glass
Indonesia
Bead producing workshop
17th to 19th c. glazed ceramics from Mexico (Ronald Bishop, Jim Blackman,NMNH).
_ Comparison of the composition of the paste and of the glaze to helplocating production centers in Mexico.
GLAZEGLAZE
the sample moves this way
pas
teg
laze
laser beam laser beam
the sample stays still
Single point analysis Scan line analysis
MgO MgO + K+ K22O O –– Na Na22O O –– CaO CaO Ternary DiagramTernary Diagramfor Majolica from Mexicofor Majolica from Mexico
1
AlAl22OO33 –– SnO SnO22 –– PbO PbO Ternary Diagram forTernary Diagram forMajolica from MexicoMajolica from Mexico
0
20
40
60
80
100
120
0 5 10 15 20 25
Nb (ppm)
Ce
(pp
m)
1
2
3
Nb Nb –– Ce Ce Graph for Majolica from MexicoGraph for Majolica from Mexico
Beginning of the ablation End of the ablation
glaze pasteinterface
Beginning of the ablation End of the ablation
glaze pasteinterface
GOLD ALLOYGOLD ALLOY
Gold ores from different parts of North, Central and South America(Paul Pohwat and Serena Sorensen, NMNH).
_ Are there specific trace element patterns according to area?
Gold plaques and foils fromChina, dated from the 6th c. BC.(Paul Jett, FGA-DCSR)
_ Is it possible to discriminategold alloy with similarcomposition using trace elementconcentrations?
California
BoliviaBrazil
French Guiana
Peru
Mexico
Puerto Rico
NicaraguaCosta Rica
No specific trace elementpatterns exist for gold orefrom the Americasaccording to the area,except for Brazilian goldthat contains high Pdcontents.
Implication: It is notpossible to trace the originof gold by comparing traceelement patterns in goldobject and gold oresexcept for some veryspecific cases.
GOLD ALLOYGOLD ALLOY
Gold ores from different parts of North, Central and South America(Paul Pohwat and Serena Sorensen, NMNH).
_ Are there specific trace element patterns according to area?
Gold plaques and foils fromChina, dated from the 6th c. BC.(Paul Jett, FGA-DCSR)
_ Is it possible to discriminategold alloy with similarcomposition using trace elementconcentrations?
Ag Ag –– Au Au –– Cu Ternary Diagram for Cu Ternary Diagram forChinese gold samplesChinese gold samples
Ag Ag –– Au Au –– Cu Ternary Diagram for Cu Ternary Diagram forChinese gold samplesChinese gold samples
Area that will be magnifiedArea that will be magnified
Ag Ag –– Au Au –– Cu Ternary Diagram for Cu Ternary Diagram forChinese gold samplesChinese gold samples
Magnified areaMagnified area
0
50
100
150
200
250
300
0 1000 2000 3000 4000 5000 6000 7000
Pd (ppm)
Pt
(pp
m)
1
2 3 ?
A least two different gold sources were used to manufacture thegold objects.
Pd - Pt Graph for the Chinese Gold SamplesPd - Pt Graph for the Chinese Gold Samples
COPPER ALLOYCOPPER ALLOY
Matisse bronzes from theBaltimore Museum of Art analyzedusing the Handheld XRF (Jia-SunTsang, Charles Tumosa, SarahPinchin, SCMRE)
_ Comparison of analytical resultsprovided by the handheld XRF andby LA-ICP-MS
Handheld XRF: surface analysisLA-ICP-MS: “core” analysis
Sn y = 6.4297xR2 = 0.9995
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0% 2% 4% 6% 8% 10%
certified values
no
rma
lize
d s
ign
al
Zn y = 1.3205xR2 = 0.9995
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.0% 1.0% 2.0% 3.0%
certified values
no
rma
lize
d s
ign
al
Pb y = 22.521xR2 = 0.9995
00.10.20.30.40.50.60.70.80.9
1
0% 1% 2% 3% 4% 5%
certified values
no
rma
lize
d s
ign
al
Ni y = 0.9034xR2 = 0.9978
0
0.005
0.01
0.015
0.02
0.025
0% 1% 2% 3%
certified values
no
rma
lize
d s
ign
al
Calibration curvesCalibration curves
Comparison for the Tin and Zinc ConcentrationsComparison for the Tin and Zinc Concentrationsbetween handheld XRF and LA-ICP-MSbetween handheld XRF and LA-ICP-MS
Determination of inorganic constituents in organic materialsDetermination of inorganic constituents in organic materials
_ Inorganic mordants or dyes on textile
_ Lead in lichen
_ and also…
… Arsenic in bone or tanned skin
MORDANTS AND DYES ON TEXTILESMORDANTS AND DYES ON TEXTILES
Modern and Ancient textiles (Mary Ballard, SCMRE)
_ Testing of the feasibility of determining mordants using ICP-MS.
Fe
01000020000300004000050000
original tin aluminum iron copper uranium
sig
nal in
ten
sit
y
Sn
0
20000
40000
60000
80000
100000
original tin aluminum iron copper uranium
sig
nal in
ten
sit
ies
Cu
0
1000000
2000000
3000000
original tin aluminum iron copper uranium
sig
nal in
ten
sit
ies
Al
0
500000
1000000
1500000
original tin aluminum iron copper uraniumsig
nal in
ten
sit
ies
U
0
2000000
4000000
6000000
8000000
original tin aluminum iron copper uranium
sig
nal in
ten
sit
ies
LEAD IN LICHENLEAD IN LICHEN
Lichens from Turkmenistan (Paula DePriest, Abdurahimova, Z., NMNH)
_ To correlate level of lead contamination with morphological changes inlichens.
_ To determine feasibility of using lichens to determine atmospheric pollutionlevels in Turkmenistan.
0
500
1000
1500
2000
a a a b c c d d e e*
species
lead
(p
pm
)
a = Physconia pulverulenta ; b = Placolecanora peltata ; c = Dermatocarpon miniatum ; d = Teloschistesbrevier ; e = Parmelia baltimorensis
Turkmenistan
Maryland
* Lawrey and Mason,1981
Lead Content According to the Provenance of the LichenLead Content According to the Provenance of the Lichen
0
10
20
30
40
50
60
a a a b c c d d e e*
species
lead
(p
pm
)
a = Physconia pulverulenta ; b = Placolecanora peltata ; c = Dermatocarpon miniatum ; d = Teloschistesbrevier ; e = Parmelia baltimorensis
Turkmenistan
Maryland
* Lawrey and Mason,1981
Lead Content According to the Lichen SpeciesLead Content According to the Lichen Species
A species retains lesslead than the others
Materials that can be routinely analyzed using:Materials that can be routinely analyzed using:
LA-ICP-MS:
Siliceous materials (glass, glaze)
Metals (gold, copper alloys)
ICP-MS:
Organic materials containing inorganic constituents
Questions that can be addressed:Questions that can be addressed:
Provenance studies
Trade exchanges
Technical skills
Authenticity verification
Level of contamination…..
Article:Article:
DUSSUBIEUX, L., VAN ZELST, L., 2004, LA-ICP-MS analysis of platinum group elements and otherelements of interest in ancient gold, Applied Physics A79, Materials Science & Processing, pp.353-356.
Conferences:Conferences:
DUSSUBIEUX, L., Analyses of Indonesian Glass Beads Using LA-ICP-MS, 10th InternationalConference of the European Association of Southeast Asian Archaeologists, London, 13-17th
September 2004.
DUSSUBIEUX, L., VAN ZELST, L., LA-ICP-MS analysis of platinum group elements and otherelements of interest in ancient gold, European Materials Research Society Meeting, June, 2003.
Accepted Papers:Accepted Papers:
DUSSUBIEUX, L., PINCHIN, S.E., TSANG, J-S., TUMOSA, C., Immediate on-the-spot non-destructive analysis: applications and reliability of the handheld XRF in the museum field, ICCOM-CC Triennial Meeting, The Hague, 2005.
DUSSUBIEUX, L., NAEDEL, D., CUNNINGHAM, R., ALDEN, H., BALLARD, M., Accuracy, precision,and investigation: mordant analysis on antique textiles by various methods, ICCOM-CC TriennialMeeting, The Hague, 2005.
DUSSUBIEUX, L., NAEDEL, D., CUNNINGHAM, R., ALDEN, H., BALLARD, M., Using ICP-MS todetect inorganic elements in organic materials: a new tool to identify mordants or dyes on ancienttextiles, Materials Research Society Fall Meeting, Boston, MA.,December, 2004.
Acknowledgements :Acknowledgements :
My successive advisors at SCMRE: Feather, M., Vandiver, P., Bishop, R.
The directors at SCMRE: Koestler, R., DePriest, P.,Vandiver, P. and Van Zelst, L.
The handheld XRF team: Tsang, J., Tumosa, C., Pinchin, S.
The SCMRE staff (in alphabetical order): Alden, H., Ballard, M., Beaubien, H.,Brostoff, L., Cunningham, R., Erhardt, D., Gluick, T., Goodway, M., Grissom, C.,Hopwood, W., Lewis, F., Mecklenburg, M., Muñoz-Alcocer, K., N’Gadi, A., Smith,B., von Endt, D., Wachowiak, M., Williams, D., Williams, V.
The fellows, interns and volunteers at SCMRE.
At FGA-DCSR: Mc Carthy, B., Jett, P.
At NMNH: Billeck, B., Burgess, L., Bishop, R., Blackman, J. and the MineralSciences Department.
At the Bead Museum, Washington, DC: Said, T., Director.
I surely forget somebody. Please accept my apologizes!
