lead and arsenic concentration in the marseille calanques ... · 1 atelier du réseau des...
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1
Atelier du Réseau des Observatoires Hommes-Milieux"Contaminations métalliques"
21 Novembre 2016
Technopôle de l'Environnement Arbois-Méditerranée, AIX en Provence
by T. Sarnet and J. Hermann
Lead and Arsenic concentration in the Marseille Calanquesmeasured by Laser Induced Breakdown Spectroscopy
LP3 Laboratory, CNRS/Aix-Marseille University, Marseille, France
Outline
- Presentation of LIBS technique
- Calibration-free LIBS developed at LP3
- Heavy metal pollution in the Calanques
Laser, Optics
and Matter
Responsable:
Olivier Uteza
Chercheur CNRS
Laser and
Plasmas
Responsable:
Jörg Hermann
Chercheur CNRS
Laser and
Biophotonics
Responsable:
Andreï Kabashin
Chercheur CNRS
Laser and
Micro-Nano
Electronics
Responsable:
Anne-P. Alloncle
Chercheur CNRS
Marc Sentis
DR1 CNRS section 10
Directeur Unité 2000-2011
Philippe Delaporte
DR1 CNRS section 10
Directeur Unité 2011-
Laser, Energy
and
Environment
Responsable:
Thierry Sarnet
Chercheur CNRS
20 permanents (80% CNRS, 20% AMU), 12 PhD/postdocs, 10 Masters/Ingénieurs
Total personnel = environ 40
UMR CNRS 7341
(Envoyé Spécial France 2 July 28, 2016 Viewers : 4 millions)
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Material analysis via LIBS
- contactless
- realtime
- no sample preparation
- almost damage free
Jean-Luc LACOUR / 2004 (CEA)
6
Jean-Luc LACOUR / 2004 (CEA)
- contactless
- realtime
- no sample preparation
- almost damage free
- hazardous environment- industrial control- material recycling- environmental survey- safety- biomedical- interplanetary exploration, …
Material analysis via LIBS
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State of art
+
+ +
+++
+-
--
-
-
--Plasma
Laser pulse Analytical performance of LIBS was demonstrated for various materials
in many cases :
LIBS measurements are qualitative or semi-quantitative
Inte
nsi
ty (
arb
. un
its)
Mg concentration (%)
Mg I 285.21 nm
Mg I 517.27 nm
0 0.5 1.0
problem = matrix effect
standards must have composition close to sample composition
8
N-BaK4
the solution :
LIBS analysis based on modeling
Outline
- Presentation of LIBS
- Calibration-free LIBS developed in LP3
- Heavy metal pollution in the Calanques
10
Calibration-free LIBS
> 100 publications (WEB of science)
First calibration-free LIBS method :
(No)
No
( )
- stoichiometric ablation
- local thermodynamic equilibrium
- plasma homogenous elemental composition
- plasma uniformin temperature and density
- plasma optically thin
+
+ +
+++
+-
--
-
-
--Plasma
Laser
hypotheses :
Ciucci et al., Appl. Spectrosc. (1999)
11
CF-LIBS method developed in LP3
100 ns
hot core
cold periphery
to spectrometer
z
Lp
Lc
to
spectrometer
T, ne
z
Lc Lp
PPPPCC LP
LLC eUeeUB
11
kThc
llu ePnfrT 1,, 0
2
0
spectral radiance :
absorption coefficient :
UV laser ablation
US patent 8942927 B2 (2015)
LTE plasma composition
T, ne, L
elemental fractions
absorption coefficient
(spectral line profile)
compare to
measured spectrum
radiation transport
(uniform or non-uniform)
12
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
13
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
1st loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
14
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
1st loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
15
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
1st loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
16
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
No
1st loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
17
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
2nd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
18
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
2nd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
19
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
2nd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
20
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
No
2nd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
21
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
3rd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
22
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
3rd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
23
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
3rd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
24
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
No
3rd loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
25
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
4th loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
26
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
4th loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
27
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
4th loop
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
28
analysis of fused silica
measure ne
arb. values
T, ne, Ci small ?
analysis finished
Yes
No
measure T
meas. composition
Yes
analysis finished
T, ne, Ci small ?
O I 777.54 nm
O I 777.42 nm
O I 777.19 nm
Si II 385.37 nm
Si II 385.60 nm
Si II 386.26 nmSi I 390.55 nm
measured
computed
NIST data
laser: 266 nm, 8 mJ100 Jcm-2
gas: argon, 5×104 Pagate: (500 ± 100) ns
Outline
- Presentation of LIBS
- Calibration-free LIBS developed in LP3
- Heavy metal pollution in the Calanques
Heavy metal pollution in the Calanques
scoria
limestonewith deposit
LIBS spectrum of limestone deposit
LIBS analysis of limestone deposit
computed
Wavelength (nm)
limestone deposit scoria
L1 L2 L3 S1 S2 S3
Arsenic (wt %) 0,5 0,09 0,1 1,3 - -
Lead (wt %) 15 13 2,5 15 1,7 1,8
35
Conclusion and outlook
LIBS works for analysis of heavy metals in environment
sensitivity > ppm, accuracy of %
LP3 is not a specialist in environment !
Development of portable LIBS for environmental survey
Contact LP3:
www.lp3.univ-mrs.fr
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History of LIBS
- 1963 : 1st publication, laser à ruby
- 4 years later : 1st apparatus by Zeiss (Germany) and Jarrel-Ash (USA)
No success low precision
- 1980’s : reliable pulsed lasers
- 1990’s : acceleration of development
LIBS development
- 2000 : 1st Conference (Pisa)
- up to now : strong increase of publications / patents
today : 20 companies commercialize LIBS systems
(USA, Germany, Japan, Italy, France, …)
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Validation on glass accurate spectroscopic data available
spectrum “easy to handle”
N-BaK4
SF5
266 nm8 mJ100 Jcm-2
5×104 Pa Argon
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Validation on glass accurate spectroscopic data available
spectrum “easy to handle” 266 nm8 mJ100 Jcm-2
5×104 Pa Argon
time
laser
detectiongate
tgate
accurate analysis for tgate < 1 µs
Gerhard et al., SAB 2014
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analysis of Ti:sapphire
CF-LIBS requires tgate < 1 µs plasma (oxygen) runs out of LTE
in agreement with glass analysis
Validation on Al2O2
accurate spectroscopic data available
spectrum “easy to handle”
Hermann et al., Phys. Rev. E 2015
analysis of Al2O3 aerosols 266 nm, 8 mJ, 100 Jcm-2
5×104 Pa Argon 1064 nm, 300 mJ1 atm helium
Boudhib et al., Anal. Chem. (2016)
41
Air
analysis ofaluminum alloy
Validation on metals
increased lifetime of LTE
CF-LIBS valid for tgate 5 µs
Argon
42
Conclusion
42
LIBS plasmas in airmolecules formed in thin cold peripheral zone atomic emission originates from plasma core peripheral zone essentially contributes through absorption
Consequences for LIBS analysis chemical reactions can be ignored if
- D0 is not “too” large (case of AlO, TiO, … )- no interference between molecular bands and lines of interest
standard CF-LIBS applicable if optically thin lines are used
LIBS plasmas in argon plasma is almost uniform chemical reactions play minor role
LIBS of organic materials chemical reactions cannot be ignored (large D0 , CN, CO, …)
challenge calibration-free LIBS of organic materials