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

Transcription

1 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

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

3 UMR CNRS 7341 Philippe Delaporte DR1 CNRS section 10 Directeur Unité Marc Sentis DR1 CNRS section 10 Directeur Unité 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

4 (Envoyé Spécial France 2 July 28, 2016 Viewers : 4 millions)

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

6 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

7 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 nm Mg I nm Mg concentration (%)

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

9 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 : 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

11 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 B2 (2015) 11 0 lu l P

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

30 Heavy metal pollution in the Calanques

31 scoria

32 limestone with deposit

33 LIBS spectrum of limestone deposit

34 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 %) ,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 35

36 Contact LP3: or

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

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

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

40 analysis of Ti:sapphire 266 nm, 8 mj, 100 Jcm 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

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

42 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