1
LASER-ASSISTED PLASMA
SPECTROMETRY IN THE ANALYSIS
OF TECHNOLOGICAL, GEOLOGICAL,
ARCHAEOLOGICAL AND
ENVIRONMENTAL SAMPLES
Viktor Kanický
Laboratory of Atomic Spectrochemistry,
Division of Analytical Chemistry,
Department of Chemistry,
Faculty of Science
Masaryk University, Brno, Czech Republic
2
• Principles and instrumentation of laser assisted
plasma spectrometry
• Applications
– Imaging of 2D-distribution of elements
– Determination of average composition (bulk analysis)
OUTLINE 1
3
1. What is laser assisted plasma spectrometry?
2. Applications:
i. technological materials;
ii. geology;
iii. archaeology;
iv. environmental.
OUTLINE 2
4
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
5
• 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
6
• 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
7
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
8
• 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
9
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
10
LA-ICP-MS/OES
[R.E. Russo, X. Mao, H. Liu, J. Gonzalez, S.S. Mao, Review, Talanta
57 (2002) 425–451]
11
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
12
Ar
laser
camera
mirror
lens
cell
tubing
displacement
x-y-z
sample
zoom
ICP Localized analysis:
laser ablation system
13
LA-ICP-MS instrumentation
LAS, Masaryk University, Brno
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
14
T. Čtvrtníčková: PhD Dissertation, Masaryk University, 2008
LIBS
15
LIBS arrangement
K. Novotný, Masaryk University
16
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
17
T. Čtvrtníčková: PhD Dissertation,
Masaryk University, 2008
orthogonal, re-heating mode
Double-pulse LIBS
K. Novotný: Masaryk University
• monochromator Jobin - Yvon
TRIAX, optical fiber,
• CCD Jobin Yvon Horiba,
• gated photomultiplier Hamamatsu
18
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
19
K. Novotný, Masaryk University
Double–pulse
orthogonal
configuration in
reheating mode
20
21
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.
22
Laser-assisted analysis of solids
• Features of laser ablation based techniques
 Elimination of decomposition for solution analysis
 Elimination of water, O, N, S, Cl from acids; resulting
species cause spectral interferences in ICP-MS
 Universal: electric conductors, non(semi)conductors
 Non-destructive: material removing from the area 10 µm2
to 1mm2 to the depth cca 0.01-0.1µm/laser pulse
 2D-3D „speciation”: preserves information on spatial
distribution of elements
23
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:
 Compact samples (steel, alloys, glass, ceramics)
 Powdered samples:
 pressed pellets with or without a binder,
 cast pellets with e.g. epoxy resin, polyurethane … ,
 melted with fusing agents for XRF  cast pearls
24
• Laser wavelength.
• Pulse energy.
• Focus position relative to surface.
• Laser repetition rate.
• Crater diameter/depth (aspect ratio).
Influencing parameters
25
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
26
Effect of laser wavelength
 Infrared laser: Nd:YAG 1064 nm
 Strongly absorbing microplasma, long interaction
 thermal effects  selective volatilisation,
fractionation
 Ultraviolet laser: ArF* 193 nm, Nd:YAG 266 nm or
193 nm
 Short interaction, minimum thermal effects,
minimum fractionation
27
Applications
28
• 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
– Study of reaction of CO2 with Na as nuclear reactor
cooling media
Technological samples
29
CORROSION OF COOLING CIRCUIT
STRUCTURAL MATERIALS OF NUCLEAR
REACTORS BY COOLING MEDIA - MOLTEN
FLUORIDE SALTS
Nuclear power station Temelín
Czech Republic
Nuclear power station Dukovany
Czech Republic
30
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:
 pure Ni,
 Ni-based alloy,
 pure Fe with Ni-coating
31
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
32
Molten fluoride salts
Sample is placed into ampoule which is filled with
molten fluoride salts for the duration of 112 and
351 hours, respectively
33
Molten fluoride salts
LA-ICP-MS experiments:
laser wavelength – 213 nm, laser spot size – 6 µm, repetition rate 20 Hz,
laser power energy density 14 J cm-2, scan rate 6 µm s-1
Steep increase of Ni signal means the start of sample surface and drop of
Na signal to background value means end of affected zone. Difference
between these two values give a thickness of affected zone. Start of
sample surface is marked as „0“.
100
1000
10000
100000
1000000
10000000
-100 0 100 200 300
distance [m]
ICP-MSsignal
Na23
Al27
Mn55
Ni60
Cu65
100
1000
10000
100000
1000000
10000000
100000000
1000000000
-500 -400 -300 -200 -100 0 100 200 300
distance [m]
ICP-MSsignal
Na23
Al27
Cr53
Ni60
Mo95
100
1000
10000
100000
1000000
10000000
-100 0 100 200 300 400
distance [m]
ICP-MSsignal
Na23
Al27
Mn55
Fe57
Ni60
Cu65
Sample Ni201
112 h
Ni201
351 h
A071EV
112 h
A071EV
351 h
Ni-coating
112 h
Ni-coating
351 h
Thickness
[m]
54 63 144 162 63 81
pure Ni Ni-based alloy pure Fe with Ni-coating
34
2D maps of corrosion of surface – testingf ampoules
35
• 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
36
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 Na2B4O7*10 H2O)
2. Dissolution of solidified sodium with water vapor –
nebulization into ICP-OES (calibration solution with NaCl,
NaNO3 and NaOH matrices)
37
Molten Na-CO2 interaction
y = 0.0087x + 9.2548
R2
= 0.9675
0
30
60
0 2000 4000 6000
carbon content [ppm]
ICP-OESintensity
NaCl
Na2B4O7
matrix matrix effect
(Imatrix/Iwater*100)
C (I) 193 nm C (I) 247 nm
NaCl 89 89
NaNO3 87 91
NaOH 74 77
C (I) 193.081 nm
y = 11.847x + 694.34
R2
= 0.9833
y = 10.623x + 794.75
R2
= 0.9987
y = 10.286x + 722.56
R2
= 0.9899
y = 8.857x + 707.6
R2
= 0.9917
0
1250
2500
0 40 80 120 160
carbon content [ppm]
ICP-OESintensity
voda
NaCl
NaNO3
NaOH
ICP-OES experiments
LA-ICP-OES experiments
carbon content [µg g-1]
LA-ICP-OES ICP-OES
Non-melted
Na
< LOD
(ca 500)
< LOD
(ca 300)
Na melted
at 300°C
3700 4050
Na melted
at 350°C
2000 3100
Na melted
at 450°C
< LOD -1
1 – not measured
38
Geology
• 2D-mapping of granite by LIBS and LA-
ICP-MS
39
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
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
40
LIBS LA-ICP-MS
Ca Fe
1 cm
K. Novotný, J. Kaiser, M. Galiová, et al.: Mapping of different structures on large area of granite sample using laserablation
based analytical techniques, an exploratory study, Spectrochimica Acta Part B 63 (2008) 1139–1144.
maps
40
photo
41
Archaeology
• Fossile bones
• Animal tooth
42
BONES ELEMENTAL MAPPING BY
LA-ICP-MS AND DOUBLE PULSE LIBS
•Radial gradient in direction from the surface towards the inner
part of compacta (dense bone) with circumferencial deviations
•Resolution among a post-mortem contamination, natural
metabolism and pathological or sanative processes
•Local analysis – determination both major and trace elements
LIBS? Luetic Tibia from ossuary in Lukavice (East Bohemia)
• single pulse – a lot of material for sufficient emission,
large craters => poor sensitivity and spatial resolution
•double pulse – small amounts of material and craters
similar to LA-ICP-MS – visible all the needed elements
43
LA-ICP-MS
Spacing: 0.15 mm, 10 × 30
craters: 0.1 mm in diameter
4.5 mm
1.5
mm
Na 23
K 39
Mn 55 Sr 88
Ba 137 Fe 56
Zn 66
Ca 44
Mg 25
Maximum
normalized -
realtive
intensity
Orthogonal double pulse LIBS
Spacing: 0.25 mm, line scan 17 craters:
0.2 mm in diameter
0
0.4
0.8
1.2
1.6
2
0 1 2 3 4
Scan line length [mm]
(X/Xmax)/(Ca/Camax)
0
1
2
3
4
5
Fe 404.58 SrII 407.77 Zn 330.29 Mg 279.55
bone
surface
0
0.5
1
1.5
2
2.5
0 1 2 3 4
Scan line length [mm]
(X/Xmax)/(Ca/Camax)
Na 589.00 BaII 455.40 K 766.49
bone surface
Ca – normalized intensities
44
Bone mapping results
• Ca, Na and P are homogenously distributed in the sample.
• Mg relative depletion in external part of the bone.
• Zn is accumulated in external part of the compact bone,
this observation is in accordance with results of other
studies. This accumulation of Zn is due to bone resorption
and osteogenesis, pathological evolutions or, due to postmortem
alterations too. In this case, correspondence with
pathological process is most probable.
• Pb, Ba are accumulated in external part of the compact
bone, similarly as zinc; Lead accumulation is due to
diagenesis.
• Sr is only slightly accumulated in periosteal region of bone
or homogenously distributed.
• Analogies in strontium, barium and lead distributions are
due to their similar metabolism
45
Bear´s tooth
The photographs of the studied sample. The investigated tooth was excavated at
Dolní Věstonice II-Western Slope, South Moravia, Czech Republic (archaeological
research in 1987) and was situated closely to the famous Upper Palaeolithic tripleburial
of young people. This locality is dated to 26 640 ± 110 BP (uncalibrated 14C
data) and belongs to Gravettian. On the left image the investigated cross section of
the analysed tooth (canin-C1) that belongs to brown bear (Ursus arctos) is shown (red
box). Increments of cementum of teeth´s root were studied in according to
determine the seasonality. This bear died at the age of 14 years in between summer
and autumn season (August to October). The bars have a length of 1 cm.
45
46
Comparison of the elemental distribution of b) Na and
c) Fe obtained on the cross-sections of fossil brown
bear (Ursus arctos) canine tooth dentine utilizing LIBS
and LA-ICP-MS. The LIBS and LA-ICP-MS line scans
were positioned to the places shown on the photograph
a).
M. Galiová, J. Kaiser, F. J. Fortes, K. Novotný, R.
Malina, L. Prokeš, A. Hrdlička, T. Vaculovič, M.
Nývltová Fišáková, J.Svoboda, J. J. Laserna:
Multielemental analysis of prehistoric animal
teeth by laser-induced breakdown spectroscopy
and Laser Ablation Inductively Coupled Plasma
Mass Spectrometry, zasláno do JASSu, 2009
46
47
The results of LA-ICP-MS elemental mapping in two different areas (a), b)) of
the sample. The bar has a length of 400 μm.
M. Galiová, J. Kaiser, F. J. Fortes, K. Novotný, R. Malina, L. Prokeš, A. Hrdlička,
T. Vaculovič, M. Nývltová Fišáková, J.Svoboda, J. J. Laserna:
Multielemental analysis of prehistoric animal teeth by laser-induced
breakdown spectroscopy and Laser Ablation Inductively Coupled Plasma
Mass Spectrometry, submitted JASS, 2009
48
The Sr/Ca and Sr/Ba ratios derived from LIBS
line scan and LA-ICP-MS mapping. With dotted
lines the different regions on the teeth cross
section are shown. The bar has a length of 500
μm.
M. Galiová, J. Kaiser, F. J. Fortes, K.
Novotný, R. Malina, L. Prokeš, A. Hrdlička, T.
Vaculovič, M. Nývltová Fišáková , J.Svoboda,
J. J. Laserna:
Multielemental analysis of prehistoric
animal teeth by laser-induced breakdown
spectroscopy and Laser Ablation Inductively
Coupled Plasma Mass Spectrometry,
submitted toJASS, 2009
49
a) estimation of the sample
hardness via magnesium ionic
to atomic line intensity ratios.
The estimated hardness
characteristic was proved by
microhardness measurements
b). The ablation crater depths
calculated from the cross
sections measured by an
optical profilometer are shown
for comparison on c).
M. Galiová, J. Kaiser, F. J. Fortes, K. Novotný,
R. Malina, L. Prokeš, A. Hrdlička, T.
Vaculovič, M. Nývltová Fišáková , J.Svoboda,
J. J. Laserna:
Multielemental analysis of prehistoric
animal teeth by laser-induced breakdown
spectroscopy and Laser Ablation Inductively
Coupled Plasma Mass Spectrometry,
submitted to JASS, 2009
49
50
root
crown
Sr
50
2,5*1,5cm
51
Environmental
• Uroliths – renal calculi
• Fish scales
52
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
53
Layered structure: growth of uroliths
54
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
55
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0 100 200 300 400 500
Time (s)
cps
Mg24 P31 Ca43 Cu63 Zn66 Pb208
43
Ca
1.0E+00
1.0E+01
1.0E+02
1.0E+03
1.0E+04
20 30 40 50 60
Time (s)
cps
43Ca 12.8%
43Ca 2.92%
Pb208 1.47
µg/g
LA started LA stopped
208
Pb
• 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
56
Calibration Zn, Pb, Cu powdered urolith pressed pellets
R
2
= 0.9844
R
2
= 0.9834
R
2
= 0.8604
0
2000
4000
6000
8000
0 1 2 3 4 5
Cu, Pb content [µg/g]
Cu,PbIntensity[count]
0
1000
2000
3000
4000
5000
0 10 20 30 40 50
Zn content [µg/g]
ZnIntensity[count]
Cu Pb Zn
57
Calibration Ca, P: powdered urolith pressed pellets
P: R
2
= 0.9516
Ca: R
2
= 0.9728
0.0E+00
2.0E+05
4.0E+05
0.0E+00 1.0E+05 2.0E+05 3.0E+05
Ca content [µg/g]
Casignal[count]
0.0E+00
3.0E+04
6.0E+04
9.0E+04
0 1000 2000 3000
P content [µg/g]
Psignal[count]
Ca P
58
Radial profile of urolith - signal
0.0E+00
1.0E+04
2.0E+04
3.0E+04
4.0E+04
0 100 200 300 400 500 600
Time [s]
Intensity[cps]
Pb208
0.0E+00
1.0E+04
2.0E+04
3.0E+04
4.0E+04
0 100 200 300 400 500 600
Time [s]
Intensity[cps]
Pb208
59
Urolith section, complementarity of apatite and
oxalate vs urate, quatification – pressed pellets
0
500
1000
1500
0 10 20 30 40 50 60 70 80
Crater No.
ContentMg,P[µg/g]
0.E+00
2.E+05
4.E+05
6.E+05
8.E+05
ContentCa[µg/g],signalC
Mg24 P31 C12 Ca43
V Konecna, M. Novackova,
M. Hola, P. Martinec, J. Machat,
V. Kanicky
60
2D graph of distribution of Ca concentration in sample 10806
Length (mm)
Width
(mm)
concentration (g/kg)
43Ca
61
2D graph of distribution of P concentration in sample
10806
Length (mm)
Width (mm)
concentration (g/kg)
31P
62
2D graph of distribution of Mg concentration in sample
10806
Width
(mm)
Lenght (mm)
concentration
(g/kg)
24Mg
63
2D graph of distribution of C presence in sample
10806
Lenght (mm)
Lenght
(mm)
intensity (cps) 12C
64
LA-
ICP-
MS
LIBS
Scanned areas of uroliths
65
LA-ICP-MS HEAVY METAL ANALYSIS OF
FISH SCALES IN SEDIMENT
• Samples - fish scales of recent fish and in the
subrecent fish scales in boreholes in the oxbow
lake sediments of the Morava River
• Analysis of subrecent and recent fish scales
• Study of fosilization process
• Comparison with sediment
Nd:YAG laser system UP 213
line of spots with a diameter of 55 μm,
30 μm s-1 scan speed, 10 Hz, Fl 5 J cm-2.
ICP-MS spectrometer Agilent 7500ce
Quantification on NIST 1486 (bone meal) and NIST 612 (glass)
Internal standard: Ca (EPXMA)
66
Markéta Holá*, Jiří Kalvoda, Ondřej Bábek, Rostislav Brzobohatý, Ivan Holoubek,
Viktor Kanický, Radek Škoda
Variation in the content of the studied elements
(grey lines) in fish scales of living fish and
subfossil fish scales in the boreholes
The substantial loss of collagen during
fossilization is very rapid and is
accompanied by extremely rapid (1 to 2
years) change in the colour from white
in recent fish scales to brown in
subrecent ones, which is connected
with the iron diffusion.
The subrecent fish scales exhibit heavy
metal concentrations:
• that are an order of magnitude higher
than in the recent ones
• but are similar to the concentrations
found in the bulk sediment.
67
CONCLUSIONS
• LA-ICP-MS analysis of compact samples without
internal standardisation is difficult but feasible.
• LIBS elemental mapping with double-pulse
technique is comparable with LA-ICP-MS
• LA-ICP-MS study of history of contamination of
nature
• Spatially resolved analysis of corroded surfaces
by LA-ICP-MS can be complementary EPXMA
• LA-ICP-OES applicable to carbon determination