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LASER ABLATION  INDUCTIVELY  COUPLED PLASMA MASS SPECTROMETRY – PRINCIPLES  AND APPLICATIONS
IN THE ANALYSIS OF ENVIRONMENTAL  GEOLOGICAL, ARCHAEOLOGICAL
 AND TECHNOLOGICAL  MATERIALS
Viktor Kanický
Laboratory of Atomic Spectrochemistry,
Division of Analytical Chemistry,
Department of Chemistry,
Faculty of Science
Masaryk University, Brno, Czech Republic
las-bile MU2 kopie

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•Principles and instrumentation of laser assisted plasma spectrometry
•Applications
–Imaging of 2D-distribution of elements
1.examples from literature;
2.research at the Department of Chemistry MU:
i.technological materials;
ii.geology;
iii.archaeology;
iv.environmental.
–Provenance study in archaelogy
•
–
–
–Determination of average composition (bulk analysis)
OUTLINE

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What is laser assisted plasma spectrometry?
•Interaction of pulsed (nanosecond, fs) laser focused beam with solids at high laser power density
(~109 W/cm2) causes rapid release of material from the surface and near-surface layer – laser
ablation
•Laser ablation results from rapid heating of sub-surface volume ⇒ high pressure of vaporized
sub–surface material brings about surface layer explosion. Besides, melting occurs.
•Released matter consists of aerosol, vapour, atoms&ions.
Laser ablation processes

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•Besides, ambient gas is ionized and forms together with ionized sample microplasma
•Laser radiation is partly absorbed in microplasma ⇒ energy transfer to atoms and ions occurs
•Absorbing microplasma existing for μ-seconds shields sample surface – attenuation of laser beam
power applied to a sample – efficiency decreases ⇒ contribution of thermal effects ⇒ undesired
melting ⇒ fractionation of elements (boiling temperatures)
•Microplasma existing for μ-seconds in contact with sample heats surface ⇒ undesired melting ⇒
fractionation of elements (boiling temperatures).
Laser ablation processes

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•Heating of gas induces shock wave (pressure, acoustic effect), microplasma expands and
extinguishes
•Cooling of microplasma causes condensation of vapours into fine aerosol droplets and
solidification of liquid droplets into coarse particles ⇒ different composition ⇒ fractionation of
elements
•Some particles (coarse, liquid droplets) fall around crater „ejecta“
•Aerosol is possible to transport with carrier gas into ICP with detection either radiation
(LA-ICP-OES) or ions (LA-ICP-MS)
•Radiation of analytes in microplasma is measured (LIBS)
Laser ablation processes

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Laser ablation process: a) laser – sample interaction; b) plasma and sample creation; c) plasma
cooling effect; d) rim deposition
Laser ablation
T. Čtvrtníčková: PhD Dissertation, Masaryk University, 2008

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•Laser assisted plasma spectrometry
–Laser Ablation Inductively Coupled Plasma Mass Spectrometry: LA-ICP-MS
–Laser Ablation Inductively Coupled Plasma Optical Emission Spectrometry: LA-ICP-OES
–Laser Induced Breakdown Spectrometry: LIBS

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Laser beam
Laser Ablation
Deposited material
Crater
Solid sample
Cracking of material
Shock wave
Heating, melting,
vaporisation, explosion
Absorption of
radiation in plasma
Vaporisation
Atomisation
Excitation
Ionisation
Atoms, ions,
clusters, aerosol
LM-OES, LIBS
Aerosol
ICP-OES
ICP-MS
Microplasma
Emission hν

LA-ICP-MS/OES
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Laser – assisted plasma spectrometry: instrumentation
•Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)
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Ar (He) into ICP-MS
Ar (He) into ablation cell

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LA-ICP-MS/OES
[R.E. Russo, X. Mao, H. Liu, J. Gonzalez, S.S. Mao, Review, Talanta 57 (2002) 425–451]

12
positioning
x-y
ICP discharge ~ ionization source for MS
 ~ emission source for OES
Focusing 0-25 mm below  the sample surface
0.7 l/min Ar (+ He), ICP-OES
0.8 l/min Ar + 1.5 l/min He, ICP-MS
lens
laser
LA-ICP-MS/OES
ablation cell
sample
Nd:YAG laser 1064 nm,
532 nm, 355 nm, 266 nm, 213 nm, 193 nm
Pulse duration 4.4 ns
Frequency 1-20 Hz
ArF* laser 193 nm
Pulse duration 20 ns
Frequency 1-20 Hz
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Ar
laser
camera
mirror
lens
cell
tubing
displacement
x-y-z
sample
zoom
ICP
Localized analysis: laser ablation system

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LA-ICP-MS instrumentation
LAS, Masaryk University, Brno
DSCN9832
Nd:YAG laser UP-213     (New Wave Resaerch)
ICP-MS Agilent 7500ce
213 nm
frequency: 1-20 Hz
pulse: 4.2 ns
spot size 4-300 µm
generator 27.12 MHz
collision cell
quadrupole mass filter
electron multiplier
supercell_photo_2 supercell_photo

Laser – assisted plasma spectrometry: instrumentation
•LA-ICP-(Q)MS at Masaryk University
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up2133.jpg icp_ms.jpg
Ablation system – UP213 (New Wave, USA)
ICP-(Q)MS
Agilent 7500 CE (Agilent, Japan)

LIBS
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T. Čtvrtníčková: PhD Dissertation, Masaryk University, 2008
LIBS

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LIBS arrangement
K. Novotný, Masaryk University

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LIBS – optimum delay time
Optimum delay time selection from signal and background intensity dependence on delay time, Al (I)
396.152 nm, background 397.5 nm; 266 nm laser (4th harmonics)
T. Čtvrtníčková: PhD Dissertation, Masaryk University, 2008

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T. Čtvrtníčková: PhD Dissertation, Masaryk University, 2008
MU_orthogonal_reheating
orthogonal, re-heating mode
Double-pulse LIBS
K. Novotný: Masaryk University
•monochromator Jobin - Yvon TRIAX, optical fiber,
•CCD Jobin Yvon Horiba,
•gated photomultiplier Hamamatsu

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Double pulse LIBS
The temporal history of LIBS
Plasma – double pulse. The delay between the pulses (interpulse separation) is Δt, the delay to the
opening of the window (delay time) td and window length (integration time) is tb

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DP blok
K. Novotný, Masaryk University
Double–pulse orthogonal configuration in reheating mode

Laser – assisted plasma spectrometry: instrumentation
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Export3 MU_orthogonal_reheating blok
Reheating
•    LIBS Double – pulse setup (DP), orthogonal configuration,   reheating arrangement  (Masaryk
University)

Laser – assisted plasma spectrometry: instrumentation
•LIBS Double – pulse setup (DP), orthogonal configuration, reheating arrangement  (Masaryk
University)
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1 – Ablation laser (New Wave, MACRO 266 nm),
2 – Reheating laser (Quantel Brilliant, 1064 nm),
3 – Sample holder and precision movements,
4 – Delay Generators (Stanford RS)
5 – Spectrometer and ICCD camera (Jobin Yvon, Triax).
4
2
3
1
5

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Export3

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Double pulse LIBS
266 nm
Optical bundle
1064 nm
A. Hrdlička, L. Prokeš, V. Konečná, K. Novotný, V. Kanický, V. Otruba
K. Novotný, J. Novotný, J. Kaizer, R. Malina, M. Galiová, V.Otruba, V.K.

Why and for what do we use laser – assisted plasma spectroscopy?
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Laser-assisted analysis of solids
•Features of laser ablation based techniques
ØElimination of decomposition for solution analysis
ØElimination of water, O, N, S, Cl from acids; resulting species cause spectral interferences in
ICP-MS
ØUniversal: electric conductors, non(semi)conductors
ØNon-destructive: material removing from the area 10 µm2 to 1mm2  to the depth cca 0.01-0.1µm/laser
pulse
Ø2D-3D „speciation”: preserves information on spatial distribution of elements

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Priorities of laser-assisted plasma spectroscopy
1)Analysis of surfaces and coatings: xy - local analysis, microanalysis, areal mapping
(mineralogical sections, inhomogeneities in steel)
2)Depth profiling of multi-layer advanced materials or natural structured objects (xyz resolution)
3)Bulk analysis:
ØCompact samples (steel, alloys, glass, ceramics)
ØPowdered samples:
vpressed pellets with or without a binder,
vcast pellets with e.g. epoxy resin, polyurethane … ,
vmelted with fusing agents for XRF Þ cast pearls

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•Laser wavelength.
•Pulse energy.
•Focus position relative to  surface.
•Laser repetition rate.
•Crater diameter/depth (aspect ratio).
Influencing parameters

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Critical parameters of LA
•Depth profiling, mapping, local analysis:
–Laser beam profile, spot size, aspect ratio,
•Bulk analysis:
– Powders: pellet preparation, cohesion and homogeneity, easy calibration
– Compacts: no preparation, homogeneity, lack of calibration samples
•Wavelength (UV´IR) vs fractionation
•Pulse duration (fs´ns) vs fractionation
Features important for particular tasks

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Effect of laser wavelength
üInfrared laser: Nd:YAG 1064 nm
üStrongly absorbing microplasma, long interaction Þ thermal effects Þ selective volatilisation,
fractionation
üUltraviolet laser: ArF* 193 nm, Nd:YAG 266 nm, 213 nm or 193 nm.
üShort interaction, minimum thermal effects, minimum fractionation.

Fractionation
1) different particle size;
2) size-dependent composition
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üFractionation I: during ablation (in situ fractionation) thermal effects Þ selective
volatilisation, smaller particles enriched with more volatile elements as they are formed by
condensation of vapours; coalescence of small particles, bigger particles by explosion of material.
üFractionation II: during particle transport bigger particles are preferentially lost;
üFractionation III: in the ICP discharge smaller particles are completely evaporated contrary to
bigger ones

Applications
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Imaging of 2D distributions of elements
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Why elemental mapping
by laser - assisted plasma spectrometry ?
•Laser - assisted plasma spectrometry:
•does not need vacuum environment in a sample compartment, and therefore allows:
–faster sample exchange/manipulation in a sample cell
–analysis of porous or wet samples;
•does not need any surface treatment prior to analysis;
•involves greater thickness of probed layer and yields more representative composition in some
cases
•provides efficient detection of light elements (Li, Be, B…).
There already exist advanced methods for mapping (SEM, EMPA, SIMS, PIXE, …), however,

Limitations of laser–assisted plasma spectrometry
•Spatial variability of composition to be mapped is associated obviously with variability of sample
physical properties in space Þ variability of ablation rate and therefore amount of ablated
material Þ matrix effect;
•Consequently, calibration is not mostly feasible even using reliable homogeneous standard samples
or CRM;
•Rather qualitative results are obtained instead of quantitative, especially in case of complex
structured samples of biological origin (biominerals, bones, plant or  animal tissues)
•Spatial resolution is poorer in comparison to particle beam based techniques (X – XX µm for laser
techniques vs. nanometers for particle beams.
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•Techniques
–Grid of isolated craters – discrete points obtained at intermittent ablation:
• ablation chamber dead volume and consequent signal tailing is not critical at LA-ICP-MS
•time consuming process
–Raster of paralell line scans – continuous ablation:
•requires fast rise and decay of signal in time – small volume of  ablation cell and tubing
•requires fast and simultaneous data acquisiton – TOF-MS or simultaneous sector analyzers
•faster analysis
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Mapping of surfaces

•Techniques
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Mapping of surfaces
15 spots in line
Ablation crater
Matrix  of discrete points: non- overlapping ablation spots
neighbouring craters

Mapping of surfaces
•Spatial resolution
–Influence of laser beam energy profile
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Nomodel10C04_27302_image001
A. Hrdlička, Ph.D. Thesis 2006

Mapping of surfaces
•Spatial resolution
–Definition (lateral or depth resolution)
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A. Hrdlička, Ph.D. Thesis 2006
1_1_abrozlis_8310_image001

Mapping of surfaces
•Examples  from liteature:
–Compact homogenized sample
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tab1
•repetition rate 10Hz,
•beam diameter 100 and 240 µm,
•scan speed 60 µm/s,
• integration time 100 ms,
•element and wavelength, (nm)
Ca 183.801, Mg 285.21,
Zn 206.200, P 177.495,
S 180.731.
www.analyticalsciences.group.shef.ac.uk/
Copyright © 2010, The University of Sheffield
LA-ICP-OES mapping of pharmaceutical tablets
Distribution of drugs and matrix

Mapping of surfaces
•Examples from liteature:
–Distribution of contrast agent (MRI) in tumor tissue
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tumor
•histology section and structure of novel Gd contrast agent (bottom),
• Laser line-raster data (1-3) shows Gd signal strength.
MRI research group at Hammersmith Hospital (Prof. J. Bell);
http://www.imperial.nhs.uk/hammersmith/index.htm
LA-ICP-MS 157Gd image distribution from thin-section of treated tumour - distribution in vascular
and necrotic areas

ratbrain
Mapping of surfaces
•Examples from literature:
–LA-ICP-MS images of quantitative distribution of Zn, Cu, Fe, K, Mn, Mg, C, P and S in a rat brain
section
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For Zn, Cu and Fe the maximum of the concentration scale bar is indicated, the minimum being zero.
J. Sab. Becker et al., Metallomics, 2010, 2, 104-111.
Quantitation is based on calibration  with standards prepared from homogenized rat brain tissue
with added standard solutions of elements

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Applications
Experimental results
 Masaryk University

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•Analysis of technological materials for nuclear power plants
–Study of corrosion of structural materials for cooling circuits of nuclear reactors by cooling
media - molten fluoride salts
Technological samples

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CORROSION OF COOLING CIRCUIT STRUCTURAL MATERIALS OF NUCLEAR REACTORS BY COOLING MEDIA - MOLTEN
FLUORIDE SALTS
jaderna-elektrarna-temelin jaderna-elektrarna-dukovany
Nuclear power station Temelín
Czech Republic
Nuclear power station Dukovany
Czech Republic

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Molten fluoride salts
Development of new types of reactors:
•Transmutor – reactor exploiting a substantial part of the long-term nuclear wastes for transfer
into useful power; cooling medium – molten fluoride mixture (LiF-NaF) attacks a surface of piping
and heat exchanger parts => corrosion processes study of sample surface by means of LA-ICP-MS
•3 structural materials for piping and heat exchangers parts are examined:
üpure Ni,
üNi-based alloy,
üpure Fe with Ni-coating

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LA-ICP-MS mapping with quantitation – corrosion layers on alloys
•Candidate structural materials were exposed to effect of mixture of molten fluoride salts
(composition in mol.%) :
•60 LiF - 40 NaF or 42 LiF - 29 NaF – 29 ZrF4
•for 112, 350 and 1000 hours
•at temperatures 680, 720 and 740 °C.
T. Vaculovic, P. Sulovsky, J. Machat, V. Otruba, O. Matal, T. Simo, Ch. Latkoczy, D. Günther and V.
Kanicky, The EPMA, LA-ICP-MS and ICP-OES study of corrosion of structural materials for a nuclear
reactor cooling circuit by molten fluoride salts treatment, J. Anal. Atom. Spectrom. 24, 649-654
(2009).

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Molten fluoride salts
2.Pressure and vacuum system
3.Oven for heating of ampoules
4.Measuring & control system
1
3
2
1.Ampoules with samples of structural material and salt
4

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Molten fluoride salts
Sample is placed into ampoule which is filled with molten fluoride salts for the duration of 112
and 351 hours, respectively
Fig1 C

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Corrosion experiment
O. Matal, T. Šimo, L. Nesvadba, V. Dvořák, V. Kanický, P. Sulovský, J. Machát, Interaction of
pipeline materials with molten fluoride salts. Zeitschrift für Naturforschung: Teil a, 62a, 12,
769-774 (2007).
Ar
Oven
Ampoule made of tested material
1-ampoule wall
2-molten fluorides
3-test specimen
4-specimen
suspension
Specimen
moved
up-and-down
periodically

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Sample preparation
molten fluoride
salt level
cut of the specimen
Test specimen
exposed in ampoule
Section of specimen embedded
in Araldite
Section with corroded surface

Electron probe microanalysis of sections and surfaces of ampules
•SX100 microprobe (CAMECA, France)
•
•Polished sections and relief specimens (inner wall of the ampule, test body surface) were imaged:
ØMorphology- Images in secondary electrons – SE
ØMaterial contrast-Images in backscattered electrons – BSE
•In order to reveal the compositional changes at the alloy/fluoride melt interface, polished
sections of ampule walls and solidified melts were investigated by EPMA, the limits of
determination being about 2 – 3x10-2 %:
ØLinear concentration profiles- X-ray analysis
Ø2D elemental concentration maps- X-ray analysis
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Damage of ampule wall by NaF/LiF melt
1.Ampule wall section 100 h exposure
2.Ampule wall section 300 h exposure
3.Ampule wall section 1000 h exposure
1.4571 STAINLESS STEEL
Images BSE
2
50 μm
1
50 μm
3
50 μm
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Depth of erosion of ampule wall
Exposure time (hours)
Red – Inconel A 686
Blue – Stainless steel 1.4571
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X-ray maps of Inconel by EPMA
X-ray map of Ni – Inconel 686, exposed to 60% LiF – 40% NaF melt for 117 hours
X-ray map of Cr – Inconel 686, exposed to 60% LiF – 40% NaF melt for 117 hours
Ni
50 μm
Cr
50 μm
High
High
Low
Low
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High
X-ray maps of Inconel by EPMA
X-ray map of Mo – Inconel 686, exposed to 60% LiF – 40% NaF melt for 117 hours
X-ray map of W – Inconel 686, exposed to 60% LiF – 40% NaF melt for 117 hours
Mo
50 μm
W
50 μm
High
Low
Low
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SE images of Inconel sample surface
Another part of the surface of Inconel 686 test body exposed to 60% LiF – 40% NaF melt for 1000
hours - area without Cr2O3 crust.
Crystalline crust of chromium trioxide (bright grey platelets) on the surface of Inconel A686
exposed to 60% LiF – 40% NaF melt for 1000 hours
100 μm
100 μm
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Results EPMA
•The Inconel 686, exposed to 60% LiF – 40 % NaF melt (1000 h, dynamic test) shows significant
compositional changes at the interface with melt. The depth to which these changes affected the
composition of the tested material, however, does not exceed 20 – 25 μm.
•The corrosion of Inconel by LiF/NaF is characterized by two processes:
–diffusion and dissolution of the alloy,
–oxidation of released Cr by traces of O2 in the Ar filling the space above the melt level.
•Fe content is homogeneously increased in the subsurface 20 – 25 μm thick layer by max. 10%
•Cr is depleted in this layer, while Ni and Mo are distinctly enriched in it.
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Laser ablation conditions :
laser beam fluency: 25.5 J cm-2
laser beam spot diameter: 12 mm
repetition rate: 20 Hz
ablation mode: hole drilling
distance between spots: 12 mm
Laser beam dwell time: 5 s
100 μm
Ablation mapping
ICP-MS
Agilent 7500 ce

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time [s]
Signal measurement
One line of ablation spots
Background correction

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Isotope signals total sum normalization
 – abundance corrected intensity
I(Mn)abund = I(55Mn)corr/abundance(55Mn)
I(Li)abund, I(Na)abund, I(Ni)abund, I(Cr)abund, ... => ∑Iabund
content Mn = [I(Mn)abund/∑Iabund ]*100 (%)
Fluoride ion counts were calculated from stoichiometry of fluoride salts and Na, Li, Zr counts
Quantitation

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distance [μm]
Zr content [%]
Ni (98 %) exposed to molten LiF-NaF-ZrF4  at 680 °C for 1000 hrs
100 μm
Zr map of „Nickel“ sample corroded surface
Corrosion layer

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Li map of „Nickel“ sample corroded surface
distance [μm]
Li content [%]
Ni (98 %) exposed to molten LiF-NaF-ZrF4  at 680 °C for 1000 hrs
100 μm
Corrosion layer

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distance [μm]
Mn content [%]
Ni (98 %) exposed to molten LiF-NaF-ZrF4  at 680 °C for 1000 hrs
100 μm
Mn map of „Nickel“ sample corroded surface

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Conclusion I
•Penetration of molten salts into specimen material was proved (signals Zr, Li, Na).
•Corrosion depth was determined from elemental maps (Zr, Li, Na)… 30 μm.
•Quantitation of elemental mapping is possible by normalization to total sum of signals for „easy“
matrix (alloys,metals, ceramics).

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Geology
•2D-mapping of granite by LIBS and LA-ICP-MS

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3A.TIF 3C.TIF
K. Novotný, J. Kaiser, M. Galiová, et al.: Mapping of different structures on large area of granite
sample using laser-ablation based analytical techniques, an exploratory study, Spectrochimica Acta
Part B 63 (2008) 1139–1144.
Exploratory study - granite
Untitled-1.tif Untitled-2.tif
42Ca, 27Al, 56Fe, 55Mn
1 cm
200 µm
LA-ICP-MS
hole drilling mode, 110 µm laser spot diameter, 20 laser pulses per sample point, distance between
individual laser spots was 200 µm
LIBS
120 µm laser spot diameter, 2 laser pulses per sample point
1 cm

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Fig.4.tif zula.jpg
LIBS               LA-ICP-MS
mapy+foto.tif
Ca                         Fe
1 cm
K. Novotný, J. Kaiser, M. Galiová, et al.: Mapping of different structures on large area of granite
sample using laser-ablation based analytical techniques, an exploratory study, Spectrochimica Acta
Part B 63 (2008) 1139–1144.
maps
70
photo

Archaeology
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Study of prehistoric bear tooth for acquiring knowledge about diet

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•Ratio 87Sr/86Sr depends on the geological substrate and Sr enters to the food chain via rock
decay. The sequence is as follows: rocks ® water ® plants ® herbivores.
•Strontium and calcium metabolism are similar and strontium can substitute calcium in
hydroxyapatite matrix.
•The fluctuation of Sr/Ca ratio enables to reconstruct the migration of an animal or human due to
environment change of ratio. Both elements have nutrition character and they are used for the
determination of diet.
Known facts
•Content of  Sr [mg/kg] in teeth and  bones (Ca10(PO4)6(OH)2) in the order
•carnivores → omnivore → herbivores → marine foodstuff is
• 100-300    → 150-400  →   400-500  → >500

Known facts
•Similar properties can be observed from Sr/Ba ratio. This fluctuation is more sensitive in
comparison with Sr/Ca due to the presence of barium. However, higher content of Ba on the surface
can indicate contamination.
•Opposite behavior was observed for zinc in comparison with Sr content. Content of Zn increases as
follows:
–herbivores ® omnivore ® carnivores
– 90-150 mg /kg1 ® 120-220 mg/kg1 ® 175-250 mg/kg.
•Higher concentration of the element is typical for meat, nuts or mollusks. On the other side, it
can be caused by inflammation.
•
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Bear tooth
126.jpg
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bear_01.tif 935795-001a.jpg fotka.tif Koren_LIBS.tif
•The investigated tooth (canine-C1) of fossil brown bear (Ursus arctos) was excavated at Dolní
Věstonice II-Western Slope, South Moravia, Czech Republic.
*
•The locality is dated to 26 640 ± 110 BP (uncalibrated 14C data) and belongs to Gravettien.
crown section
root section
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 Bear tooth
medved.jpg
76
935795-001a.jpg
•Abrasion of tooth´s oclusal area and increments of cementum of tooth´s root were studied in order
to determine the age and seasonality.
•
•This bear died at the age of 14 years and it is possible to appoint the term of death from
unfinished summer increment and absence of winter increment in between summer and autumn season
(August to October).
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mikrotvrdost_koren.TIF
77
barevna skala.tif pomerMg_koren.tif
2 mm
•The estimation of the sample hardness via Mg II/Mg I intensity ratios is shown.
•The estimated hardness characteristic was proved by microhardness measurements.
•The Vickers test pattern was placed nearby the LIBS ablation craters for Mg detection.
pomerMg_koren_rada.TIF
Hardness of the sample (canine tooth root)
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Sr_Ba_koren_DP.tif Sr_Ca_koren_DP.tif barevna skala.tif
DP LIBS
Sr/Ba
Sr/Ca
Koren_LIBS.tif
The dark areas on the sample are well correlated with the lower Sr/Ba Sr/Ca ratio in the map. They
are rather related to the narrow winter strips.
Ethology of the studied fossil brown bear
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SP and DP LIBS and LA-ICP-MS

Sr_Ca_koren_SP.tif Sr_Ba_SP.tif
79
barevna skala.tif
Sr/Ba
SP LIBS
Sr/Ca
Koren_LIBS.tif
The seasonal fluctuations of the Sr/Ca and Sr/Ba detected by laser-ablation based techniques (SP
and DP LIBS and LA-ICP-MS) evidenced the migration of this bear between his hibernaculum’s location
and the place where the fossils were found.
Ethology of the studied fossil brown bear
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SP and DP LIBS and LA-ICP-MS

C:\Documents and Settings\Administrator\Plocha\DP\zub_medved\Appl Optics_medved\Appl
Optics\Sent\Figures\Fig_7.tif
Ethology of the studied fossil brown bear
LA-ICP-(Q)MS
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44Ca.tif pomer86Sr138Ba.tif pomer86Sr64Zn.tif pomer86Sr44Ca.tif bear_root.tif
LA-ICP-(TOF)MS
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86Sr/64Zn
86Sr/138Ba
44Ca
86Sr/44Ca

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Environmental
•Uroliths – renal calculi

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 UROLITH LOCAL ANALYSIS
Kidney stones, urinary stones (renal calculi, urolithiasis) = solid concretions (crystal
aggregations) of dissolved minerals in urine calculi typically form inside kidneys, ureter,
urethra, bladder, prostate
To date over 200 components have been found in calculi; however, the most common constituents of
kidney stones are:
•Calcium Oxalate Monohydrate (Whewellite); CaC2O4 · H2O
•Calcium Oxalate Dihydrate (Weddellite); CaC2O4 · 2H2O
•Magnesium Ammonium Phosphate Hexahydr. (Struvite); MgNH4PO4 · 2H2O
•Ca Phosphate &Carbonate (Carbonate Apatite); Ca10(PO4 · CO3OH)6(OH)2
•Calcium Phosphate, Hydroxyl Form (Hydroxyl Apatite); Ca10(PO4)6(OH)2
•Calcium Hydrogen Phosphate Dihydrate (Brushite); CaHPO4 · 2H2O
•Uric Acid; C5H4N4O3
•Cystine; (SCH2CH(NH2) · COOH)2
•Sodium Acid Urate; C5H3N4O3Na · H2O
•Tricalcium Phosphate (Whitlockite); Ca3(PO4)2
•Ammonium Acid Urate; NH4H · C5H2O3N4 · H2O
•Magnesium Hydrogen Phosphate Trihydrate (Newberyite); MgHPO4 · 3H2O

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Layered structure: growth of uroliths

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Designed procedure
1.Average elemental  contents in uroliths  by PN-ICP-MS after acid mixture decomposition
2.LA-ICP-MS  calibration with homogenized urolith pellets and assignment of content values found
using PN-ICP-MS to the pellets.
3.LA-ICP-MS calibration with pressed pellet of powdered SRM NIST 1486 Bone Meal.
4.LA-ICP-MS elemental distribution recording = line of single-spot ablation events directed
perpendicularly to layered structure of urolith section
5.LA-ICP-MS calibration using:
•NIST 1486 Bone Meal
•urolith pellets with contents by PN-ICP-MS
•NIST 612 Glass
6.Calculation of concentration profile of uroliths
Agilent 7500ce
NIST 612 Glass
Urolith sections
NIST 1486 Bone Meal
Urolith pellet

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•Lines of single spots
•Laser spot size 55 /um
•Crater distance 110 /um
•Repetition rate 20 Hz
•Fluence of 3 J cm-2
•No internal standard ICP-MS

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Calibration Zn, Pb, Cu powdered urolith pressed pellets

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Calibration Ca, P: powdered urolith pressed pellets

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Radial profile of urolith - signal

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Urolith section, complementarity of apatite and oxalate vs urate, quatification – pressed pellets
V Konecna, M. Novackova,
M. Hola, P. Martinec, J. Machat, V. Kanicky

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2D graph of distribution of Ca concentration in sample 10806
Length (mm)
Width (mm)
concentration (g/kg)
43Ca

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2D graph of distribution of P concentration in sample 10806
Length (mm)
Width (mm)
concentration (g/kg)
31P

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2D graph of distribution of Mg concentration in sample 10806
Width (mm)
Lenght (mm)
concentration (g/kg)
24Mg

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2D graph of distribution of C presence in sample 10806
Lenght (mm)
Lenght (mm)
intensity (cps)
12C

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LA-ICP-MS
LIBS
Scanned areas of uroliths

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Provenance study -Archaeology
•Application of laser ablation–based methods and multivariate statistics to provenance studies of
artifacts
•

OUTLINE
•Archaeometry – study of artifacts
•Application of LA-ICP-MS to study of obsidian artifacts
•Samples
•LA-ICP-MS analysis
•Statistical treatment of data
•
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ARCHAEOMETRY
ØArchaeological science or Archaeometry consists in the application of techniques of natural
sciences to the analysis of archaeological materials. ØArchaeometry involves dating and studying
ancient materials. [1] 1.Killick, D; Young, SMM (1997). Archaeology and Archaeometry: From Casual
Dating to a Meaningful Relationship?. Antiquity.
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Archaeometry
•Comprises: [2]
Øphysical and chemical dating methods
Øartifact studies
Øenvironmental studies on past landscapes, climates, flora, fauna; the diet, nutrition and health
of beings
Ømathematical methods for data treatment
Øremote sensing and geophysical survey for the location and characterization of buried features
Øconservation sciences for the study of decay processes; development of methods for conservation
Øtechniques such as lithic analysis, archaeometallurgy, paleoethnobotany, palynology,
zooarchaeology
2.Tite, M.S. (1991) Archaeological Science - past achievements and future prospects. Archaeometry
31 139-151.
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Artifact studies
•XRF X-ray fluorescence spectrometry
•ICP-MS inductively coupled plasma mass spectrometry
•NAA neutron activation analysis
•SEM scanning electron microscopy
•LIBS laser induced breakdown spectrometry
•Provenance analysis
• has the potential to determine the original source of the materials used to make a particular
artifact.
•
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APPLICATION OF LA-ICP-MS
IN ARCHAEOMETRY – ANALYSIS
OF OBSIDIAN ARTIFACTS
ØObsidian is a naturally occurring volcanic glass formed as an extrusive igneous rock.
ØIt is produced when felsic lava extruded from a volcano cools rapidly without crystal growth.
Ø Because of this lack of crystal structure, obsidian blade edges can reach nearly molecular
thinness:
Øancient use as projectile points and blades
Ømodern use as surgical scalpel blades
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Øa glassy volcanic rock, homogeneous in bulk & surface, reflecting the volcanic environment where
it was produced;
Øraw material for prehistoric people (paleolith, neolith, 9 000 B.C. Mesopotamia, later Mayas,
Aztecs) because of the ability to produce extremely sharp cutting edge;
Østudy of composition of obsidian tools and material from the original geological source makes it
possible to learn about:
•exchange centers, trade routs;
•organization of life (hunting, craft)
Ø
Ø
Obsidians: rock and artifact
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Viničky, Slovakia
Kašov, Slovakia
E. Švecová: Bachelor thesis, Sources of obsidian in Central Europe and possibilities of their
differentiation, Masaryk University, 2009.
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Chemical analysis
of obsidians
Øchemical analysis can yield information on composition of both natural sources and artifacts
Øsolution analysis can be performed for raw material x artifacts
Ønon- destructive analysis is required for artifacts: (XRF, NAA, LA-ICP-MS, LIBS)
ØLA-ICP-MS: quasi non-destructive, simple sample preparation, applicable to small samples (1 mm),
relatively rapid determination
–
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LA-ICP-MS analysis of obsidians
•LA-ICP-MS is used for analysis of obsidians
105
3.Eerkens J. W., Spurling A. M., Gras M, A., Measuring prehistoric mobility strategies based on
obsidian geochemical and technological signatures in the Owens Valley, California, Journal of
Archaeological Science 35 (2008)668-680.
4.Whitaker A. R., Eerkens J. W., Spurling A. M., Smith E. L., Gras M. A., Linguistic boundaries as
barriers to exchange, Journal of Archaeological Science 36 (2007)1-10.
5.Gratuze B., Obsidian characterization by LA-ICP-MS and its application to prehistoric trade in
the Mediterranean and the Near East: Sources and distribution of obsidian within the Aegean and
Anatolia, Journal of Archaeological Science 26 (1999)869-881.
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ØDevelopment of method LA-ICP-MS
ØAnalysis of artifacts from various areas
ØSelection of elements applicable to distinguish between archaelogical sites
ØStatistical analysis – distinguishing between areas of archaelogical discovery of artifacts
Ø
Ø
•
•
•
AIM OF STUDY
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[USEMAP]
1
2
3
4
Provenance of samples: 1 – Czech Rep., 2 – Slovakia, 3 – Greece,
4 – Italy, Lipari island
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[USEMAP]
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ITALY
SICILY
LIPARI
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[USEMAP]
Provenance of samples: Syria, Iraq
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Czech Republic
artifacts
Breznik
Horakov
Jaromerice
Moravske Branice
Nova Dedina
Popuvky
Prstice
Rozdrojovice
Spytihnev
Tesetice I
Tesetice II
U Kr. Borovice
Zebetin
Slovakia
artifacts
Kasov I
Kasov II
source
Barca
Vinicky
Mala Bara
Italy
artifact
La Castagne
(Lipari)
Greece
artifact
Sesklo
Syria
artifacts
Tell Arbid I
Tell Arbid II
Tell Arbid III
Iraq
artifacts
Tell Asmar I
Tell Asmar II
Nicaragua
artifacts
Sebaco
Somoto I
Somoto II
Mexico
source
List of samples
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%
Barca
Lipari
Vinicky
SiO2
75.83
73.32
75.89
Al2O3
13.17
13.20
13.22
Fe2O3
1.05
1.77
0.98
CaO
0.82
0.87
0.82
MgO
0.12
0.05
0.07
Na2O
3.65
4.04
3.66
K2O
4.56
5.27
4.57
TiO2
0.05
0.08
0.05
P2O5
0.03
0.02
0.03
MnO
0.05
0.07
0.05
Composition of obsidians
 ACME reference analysis
Acme Analytical Laboratories (Vancouver) Ltd., 1020 Cordova St. East Vancouver BC V6A 4A3 Canada,
www.acmelab.com
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mg kg-1
Barca
Lipari
Vinicky
Hf
2.8
6.4
2.8
Nb
9.9
35.0
9.7
Rb
188.2
305.3
191.1
Sr
74.1
19.3
72.9
Ta
1.5
2.4
1.5
Th
16.6
58.7
17
U
10
16.9
9.9
Zr
75.4
178.4
71.2
Y
33.8
41.0
33.7
La
25.6
63.3
25.8
Ce
49.5
127.5
49.1
Pr
6.05
13.04
6.05
Nd
21.9
43.9
21.5
Sm
4.28
8.20
4.27
Eu
0.34
0.14
0.37
Gd
4.04
6.41
4.07
Tb
0.82
1.15
0.81
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LA-ICP-(Q)MS
Ablation system – UP 213 Nd:YAG (New Wave, USA)
•ablation chamber – SuperCell 20 cm3 (New Wave, USA)
•diameter of ablation craters – 100 mm;
•laser repetition rate 20 Hz;
•fluence 5 J cm-2;
•1 l/min He carrier through ablation cell
•data acquisition: 120 s (50 s ablation), 10 spots
ICP-MS Agilent 7500 CE (Agilent, Japan)
•carrier gas flow 0.6 l/min Ar
•collison-reaction cell: He 5,5 ml/min and H2 2,5 ml/min
Calibration
NIST 612
NIST 610
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Dodat podminky, při kterych linda merila

Graph2.tif
ICP-(Q)MS signal
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Vinicky, Slovakia: SiO2 75.89 %, Dy 4.58 mg kg-1, Ce 49.1 mg kg-1(ACME)
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Ablation system – UP 213 Nd:YAG (New Wave, USA),
•ablation chamber – SuperCell 20 cm3 (New Wave, USA);
•diameter of ablation craters – 100 mm;
•laser repetition rate 10 Hz;
•fluence 16 J cm-2;
•300 ml/min He carrier through ablation cell
•data acquisition: after 5 s sample uptake1 second measurement in 5 spots.
ICP-MS – OptiMass 8000 (GBC Australia)
•plasma gas flow 10 l/min Ar
•auxiliary gas flow 0.5 l/min Ar
•nebulizer gas flow  1.02 l/min Ar
•sampling depth 10 mm
LA-ICP-(TOF)MS
Calibration
NIST 614
NIST 612
NIST 610
NIST GB
P1070713.JPG P1070711.JPG
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Dodat fotku-popis

Ti,Mn,Fe_novy.tif
Czech Republic
Slovakia
Nicaragua
Content of Ti, Mn, Fe obtained
by LA-ICP-MS
Mexico
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Content of Zr, Sr, Ba obtained
 by LA-ICP-MS
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Czech Republic
Slovakia
Nicaragua
Mexico
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Content of Ce, Dy, Sm obtained
 by LA-ICP-MS
Ce,Dy,Sm_novy.tif
Czech Republic
Slovakia
Nicaragua
Mexico
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LA-ICP-MS vs. ACME
Element
Literature
ACME
LA-ICP-MS
mg kg-1
Y
35
33.70
32.71
Zr
66
71.20
60.33
La
24.4-30.4
25.80
25.54
Ce
49.10
55.20
Pr
6.05
5.78
Sm
3.68-4.32
4.27
4.14
Eu
0.41-0.52
0.37
0.38
Gd
4.07
4.27
Tb
0.44-0.84
0.81
0.73
Yb
2.82-3.65
2.96
2.96
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Vinicky obsidian sample
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STATISTICAL ANALYSIS
120
Two-way cluster analysis: data matrix is reoreded  after the results of cluster analysis on objects
(samples) and variables (elements). The output of this method is „heat map“.
R –statistical package (http://cran.r-project.org/), released under the GNU General Public License.
http://www.sciviews.org/_style/img/RLogo.png
Principal component analysis: linear transformation of the (correlated) characteristics (elements)
of the data matrix into non-correlated principal components. The most information about the
variability in original data matrix involved the first PC (see screeplot).

 PCA Loadings: reflects the relations between the original variables and between the original
variables and principal components. Cosines of the angles in the plot of the PCA loadings are
related to the correlation coefficients.
PCA Scores:  the coordinates of the objects (samples) in the space of PCs.
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Statistical analysis
•Correspondence analysis (CA): the method is commolnly used for analysis of categorical data, but
may be useful as a visualization technique for the analytical data. The method is similar to PCA,
but in CA the data are transformed to the „compositional data“ (vectors of proportions describing
the relative contributions of each of the categories to the whole) for both rows and columns of the
data matrix. The method enable, contrary to PCA, simultaneous depiction of  the results for samples
and elements in one plot.
•The results of Principal Component Analysis and Correspondence Analysis were used for the
selection of pairs of elements or their ratios for scatterplots.
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Heat map: two-way cluster analysis
122
Results od two-way cluster analysis of the autoscaled data (manhattan distances, average linkage
clustering). The results of cluster analysis are significantly influenced with correlations in the
data.
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bezpopCAscree.bmp
Correspondence analysis (CA)
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Correspondence analysis was performed on the mean-normalized data matrix. The breakpoint on the
scree plot indicates two important dimensions, involving more than 80 per cent of total inertia of
the data.
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C:\Documents and Settings\Administrator\Plocha\obsid\popisky.bmp bezpopCA.bmp
Correspondence analysis (CA)
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Correlation matrix (Pearson), reordered with average linkage clustering.
Correlation matrix (Pearson)
bezpop corrP.bmp
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bezpopPCAscree.bmp
Principal Component Analysis (PCA)
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Principal components were calculated from autoscaled data matrix. The breakpoint on the scree plot
indicates two important PCs, involving about 80 per cent of total variance of the data.
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bezpopPCAloadings.bmp
PCA loadings reflects correlations of elements in data matrix and contribution of the each element
to the each of 2 principal components (cosines of the angles between elements or between elements
and axes of PCs, respectively).
Principal Component Analysis (PCA)
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bezpopPCAscores.bmp
PCA scores are coordinates of the samples in the space of the principal components.
C:\Documents and Settings\Administrator\Plocha\obsid\popisky.bmp
Principal Component Analysis (PCA)
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bezpopDyZn.bmp
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bezpopSrNb.bmp
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bezpopZrBa.bmp
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C:\Documents and Settings\Administrator\Plocha\bezpop\bezpopCeEr.bmp
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C:\Documents and Settings\Administrator\Plocha\bezpop\bezpopSrBa.bmp
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C:\Documents and Settings\Administrator\Plocha\bezpop\bezpopUCe.bmp
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C:\Documents and Settings\Administrator\Plocha\bezpop\bezpopHfZrBaSr.bmp
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C:\Documents and Settings\Administrator\Plocha\pcach.png

modified item
var.
height of face
Sr
width of face
Ba
structure of face
Sc
height of mouth
Pb
width of mouth
Zn
smiling
U
height of eyes
Eu
width of eyes
Rb
height of hair
Nb
width of hair
Ta
style of hair
Gd
height of nose
Hf
width of nose
Ce
width of ear
La
height of ear
Nd
The elements were chosen and sorted after the increasing value of the PC1 loadings.
Chernoff faces
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CONCLUSION
137
ØCalibration of LA-ICP-MS obsidian analysis using NIST reference materials yields concentration
data that are in agreement with solution analysis (ACME)
ØPrincipal Component Analysis (PCA) and Correspondence Analysis (CA) are suitable as exploratory
data analysis methods for the purpose of this study.
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ONGOING WORK
138
ØVerification of the results of statistical analysis on large-scale data series
ØTesting some other multivariate statistical and visualization techniques.
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ACKNOWLEDGEMENT
L. Prokeš, L. Zaorálková, A. Hrdlička, T. Vaculovič, A. Prichystal, M. Galiová, K. Novotný
Dep. of Chemistry and Dep. of Geological Sciences , Faculty of Sciences, Masaryk University,
Kotlářská 2, 611 37 Brno, Czech Republic
bnr_urd2_budgetcentral.jpg
A. Z. Mason, H. Neff
Department of Biological Sciences, Faculty of Sciences, California State University Long Beach,
1250 Bellflower Blvd, Long Beach 90840, USA
The authors acknowledge support from the Ministry of Education, Youth and Sports of the Czech
Republic (projects ME10012, MSM0021622411, MSM0021622412 and MSM0021622427).
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Aknowledgements
to my collaborators
•Masaryk Univ.
•Karel Novotný
•Markéta Holá
•Tomáš Vaculovič
•Aleš Hrdlička
•Lubomír Prokeš
•Michaela Galiová
•Monika Nováčková
•Veronika Konečná
•Tereza Čtvrtníčková
•Tereza Warchilová
•Tech. Univ. Brno
• Jozef Kaiser
•University of Malaga
•X. Laserna

mapa_evropy
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mapa
Czech Republic
area: 78 864 km2, inhabitans: 10.3 millions
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1_pohled05 1_pohled07 1_jakub02 1_pohled06 Katedrála sv. Petra a Pavla
Brno
inhabitans: 370 000
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Masaryk University Campus (Brno)
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Detail fotografie Detail fotografie
Fac.of Science
Faculty of Medicine
Faculty of Sport Studies
http://www.muni.cz/general/events/p233332/gallery

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Detail fotografie
Masaryk University Campus
Detail fotografie

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Detail fotografie Detail fotografie
Masaryk University Campus
Detail fotografie

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Detail fotografie Detail fotografie
Masaryk University Campus

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Detail fotografie Detail fotografie
Masaryk University Campus

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Thank you for your attention
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•Sodium-cooled fast reactor (SFR) – Generation IV of nuclear reactors; cooling medium – liquid
sodium; heat is transferred from sodium circuit in heat exchanger to CO2 . Possible reaction of
sodium with CO2 at elevated temperatures is experimentally studied => determination of carbon in
sodium by means of LA-ICP-OES and ICP-OES
REACTION OF CO2 WITH SODIUM - NUCLEAR REACTOR COOLING MEDIA
T. Vaculovič*, V. Kanický, O.Matal

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Molten Na-CO2 interaction
A new apparatus was designed for sodium melting under CO2 atmosphere at high temperature.
Apparatus is placed into glove box with CO2 atmosphere.
Furnace is heated up to 300, 350 and 450 °C, respectively.
180 minutes of melting + 120 min cooling down
Two ways of carbon content determination
1.Laser ablation of solidified sodium with ICP-OES detection (calibration pellets with two types of
matrix – NaCl and NaF)
2.Dissolution of solidified sodium with water vapor – nebulization into ICP-OES (calibration
solution with NaCl, NaNO3 and NaOH matrices)

Glove box for:
 1) Na purity determination by distillation in Ar atmosphere: residual
     carbonate and oxide dissolved and Na determined ICP-OES
2)  Reaction of Na with carbon dioxide in CO2 atmosphere
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1 – distillation chamber
2 – temperature measure.
3 – membrane pump
4 – two-stage oil pump
5 – pressure sensor
      (workspace)
6 – pressure sensor
     ( input press. in pump)
7 – vent
8 – pressure measurement
9 – preparation box
10 – interface chambe
11 – Ar input
12 – input vent
13 – output vent
14 – manometer of interface
15 – power meter
16 – Ar control

158
jobin
Ø ICP-OES Jobin Yvon
Ø Model Ultrace 170
Ø 40.68 MHz, 0.6 – 1.200 kW
Ø Observation lateral
Ø mono.: 1-m Czerny-Turner
Ø poly.: 0.5-m Paschen Runge
Ø SBW: 4-5 pm / 20-25 pmBW
Ø detectors: photomultipliers
ØPTFE sample introduction system + corundum injector
ICP-OES
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Universidad de La Laguna

Laser ablation system
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up213

LA-ICP-OES
conditions of measurement
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LA parameters
Laser wavelength/nm
266
Laser spot diameter/µm
750
Laser power density/(J cm−2)
4.7
Laser repetition rate/Hz
10
Carrier gas (argon) flow rate/(L min−1)
0.8
ICP-OES parameters
RF power input/W
1200
Observation
Lateral viewing; 15 mm above load coil
Gas (argon) flow rates/(L min−1)
outer: 12.0; intermediate: 0.6; sheath: 0.2; carrier: 0.6

LA-ICP-OES results
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Matrix
NaF
NaCl
T/°C
300
450
600
300
450
600
CC-1L/%
0.81 ± 0.09
1.2 ± 0.1
1.5 ± 0.1
0.84 ± 0.07
1.3 + 0.09
1.6 ± 0.1
CC-2L/%
0.17 ± 0.03
0.87 ± 0.09
1.2 ± 0.1
0.18 ± 0.02
0.93 ± 0.08
1.3 ± 0.2
CC-3L/%
0.10 ± 0.01
0.47 ± 0.07
1.0 ± 0.1
0.11 ± 0.02
0.50 ± 0.08
1.1 ± 0.1
a) Content of carbon in: first layer – CC-1L, second layer – CC-2L, and third layer – CC-3L.