Lead and Arsenic concentration in the Marseille Calanques measured by Laser Induced Breakdown Spectroscopy. by T. Sarnet and J.

Atelier du Réseau des Observatoires Hommes-Milieux "Contaminations métalliques" 21 Novembre 2016 Technopôle de l'environnement Arbois-Méditerranée, AIX en Provence Lead and Arsenic concentration in the Marseille Calanques measured by Laser Induced Breakdown Spectroscopy by T. Sarnet and J. Hermann LP3 Laboratory, CNRS/Aix-Marseille University, Marseille, France 1

Outline - Presentation of LIBS technique - Calibration-free LIBS developed at LP3 - Heavy metal pollution in the Calanques

UMR CNRS 7341 Philippe Delaporte DR1 CNRS section 10 Directeur Unité 2011- Marc Sentis DR1 CNRS section 10 Directeur Unité 2000-2011 Laser, Optics and Matter Laser and Plasmas Laser, Energy and Environment Laser and Biophotonics Laser and Micro-Nano Electronics Responsable: Olivier Uteza Chercheur CNRS Responsable: Jörg Hermann Chercheur CNRS Responsable: Thierry Sarnet Chercheur CNRS Responsable: Andreï Kabashin Chercheur CNRS Responsable: Anne-P. Alloncle Chercheur CNRS 20 permanents (80% CNRS, 20% AMU), 12 PhD/postdocs, 10 Masters/Ingénieurs Total personnel = environ 40

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Material analysis via LIBS - contactless - realtime - no sample preparation - almost damage free Jean-Luc LACOUR / 2004 (CEA) 5

Material analysis via LIBS - contactless - realtime - no sample preparation - almost damage free - hazardous environment - industrial control - material recycling - environmental survey - safety - biomedical - interplanetary exploration, Jean-Luc LACOUR / 2004 (CEA) 6

Intensity (arb. units) State of art Laser pulse + - Plasma - - + + + - + - + - + - Analytical performance of LIBS was demonstrated for various materials in many cases : LIBS measurements are qualitative or semi-quantitative problem = matrix effect standards must have composition close to sample composition Mg I 285.21 nm Mg I 517.27 nm 7 0 0.5 1.0 Mg concentration (%)

the solution : LIBS analysis based on modeling N-BaK4 8

Outline - Presentation of LIBS - Calibration-free LIBS developed in LP3 - Heavy metal pollution in the Calanques

Calibration-free LIBS > 100 publications (WEB of science) First calibration-free LIBS method : Ciucci et al., Appl. Spectrosc. (1999) hypotheses : - stoichiometric ablation Laser - local thermodynamic equilibrium ( ) Plasma + - - - + + + - + - + - + - - plasma homogenous elemental composition - plasma uniform in temperature and density - plasma optically thin (No) No 10

CF-LIBS method developed in LP3 UV laser ablation 100 ns L p to spectrometer z cold periphery T, n e to spectrometer L c hot core z L c L p T, n e, L elemental fractions LTE plasma composition absorption coefficient (spectral line profile) radiation transport (uniform or non-uniform) compare to measured spectrum spectral radiance : C C LC P LP P LP 1 e e U e B U 1 absorption coefficient : 2 hc kt, T r f n P 0, 1 e US patent 8942927 B2 (2015) 11 0 lu l P

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 12

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 1 st loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 13

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 1 st loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 14

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 1 st loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 15

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 1 st loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 16

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 2 nd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 17

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 2 nd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 18

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 2 nd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 19

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 2 nd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 20

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 3 rd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 21

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 3 rd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 22

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 3 rd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 23

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 3 rd loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 24

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 4 th loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 25

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 4 th loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 26

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm 4 th loop arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 27

analysis of fused silica Si I 390.55 nm measured computed Si II 385.37 nm Si II 385.60 nm Si II 386.26 nm arb. values O I 777.42 nm No measure n e measure T meas. composition T, n e, C i small? Yes O I 777.19 nm O I 777.54 nm laser: 266 nm, 8 mj 100 Jcm -2 gas: argon, 5 10 4 Pa gate: (500 ± 100) ns NIST data analysis finished 28

Outline - Presentation of LIBS - Calibration-free LIBS developed in LP3 - Heavy metal pollution in the Calanques

Heavy metal pollution in the Calanques

scoria

limestone with 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

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 35

Contact LP3: sarnet@lp3.univ-mrs.fr or hermann@lp3.univ-mrs.fr www.lp3.univ-mrs.fr

History of LIBS - 1963 : 1 st publication, laser à ruby - 4 years later : 1 st apparatus by Zeiss (Germany) and Jarrel-Ash (USA) No success low precision - 1980 s : reliable pulsed lasers LIBS development - 1990 s : acceleration of development - 2000 : 1 st Conference (Pisa) - up to now : strong increase of publications / patents today : 20 companies commercialize LIBS systems (USA, Germany, Japan, Italy, France, ) 37

Validation on glass accurate spectroscopic data available spectrum easy to handle N-BaK4 266 nm 8 mj 100 Jcm -2 5 10 4 Pa Argon SF5 38

Validation on glass accurate spectroscopic data available spectrum easy to handle laser t gate detection gate time 266 nm 8 mj 100 Jcm -2 5 10 4 Pa Argon accurate analysis for t gate < 1 µs 39 Gerhard et al., SAB 2014

analysis of Ti:sapphire 266 nm, 8 mj, 100 Jcm -2 5 10 4 Pa Argon Validation on Al 2 O 2 accurate spectroscopic data available spectrum easy to handle analysis of Al 2 O 3 aerosols 1064 nm, 300 mj 1 atm helium Hermann et al., Phys. Rev. E 2015 Boudhib et al., Anal. Chem. (2016) in agreement with glass analysis 40 CF-LIBS requires t gate < 1 µs plasma (oxygen) runs out of LTE

Validation on metals analysis of aluminum alloy Argon Air increased lifetime of LTE CF-LIBS valid for t gate 5 µs 41

Conclusion LIBS plasmas in air molecules 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 - D 0 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 D 0, CN, CO, ) challenge calibration-free LIBS of organic materials 42