DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES

Abstract

Ancient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water-deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser-induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiosity's ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. Here, we performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam-like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate salts found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. The data then indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrixmore » and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation-anion pairing in the salt but appears relatively independent of matrices tested, following normalization. Our results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2];  [1]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [5];  [2];  [3]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. Inst. for Research in Astrophysics and Planetology (IRAP), Toulouse (France)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Mount Holyoke College, South Hadley, MA (United States). Dept. of Astronomy
  5. German Aerospace Center (DLR), Berlin (Germany)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
National Aeronautics and Space Administration (NASA)
OSTI Identifier:
1396140
Report Number(s):
LA-UR-17-27680
Journal ID: ISSN 2169-9097
Grant/Contract Number:  
AC52-06NA25396; DGE-11444469
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Geophysical Research. Planets
Additional Journal Information:
Journal Volume: 122; Journal Issue: 4; Journal ID: ISSN 2169-9097
Publisher:
American Geophysical Union
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; Planetary Sciences

Citation Formats

Anderson, D. E., Ehlmann, B. L., Forni, O., Clegg, S. M., Cousin, A., Thomas, N. H., Lasue, J., Delapp, D. M., McInroy, R. E., Gasnault, O., Dyar, M. D., Schröder, S., Maurice, S., and Wiens, R. C. Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES. United States: N. p., 2017. Web. doi:10.1002/2016JE005164.
Anderson, D. E., Ehlmann, B. L., Forni, O., Clegg, S. M., Cousin, A., Thomas, N. H., Lasue, J., Delapp, D. M., McInroy, R. E., Gasnault, O., Dyar, M. D., Schröder, S., Maurice, S., & Wiens, R. C. Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES. United States. https://doi.org/10.1002/2016JE005164
Anderson, D. E., Ehlmann, B. L., Forni, O., Clegg, S. M., Cousin, A., Thomas, N. H., Lasue, J., Delapp, D. M., McInroy, R. E., Gasnault, O., Dyar, M. D., Schröder, S., Maurice, S., and Wiens, R. C. Mon . "Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES". United States. https://doi.org/10.1002/2016JE005164. https://www.osti.gov/servlets/purl/1396140.
@article{osti_1396140,
title = {Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES},
author = {Anderson, D. E. and Ehlmann, B. L. and Forni, O. and Clegg, S. M. and Cousin, A. and Thomas, N. H. and Lasue, J. and Delapp, D. M. and McInroy, R. E. and Gasnault, O. and Dyar, M. D. and Schröder, S. and Maurice, S. and Wiens, R. C.},
abstractNote = {Ancient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water-deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser-induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiosity's ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. Here, we performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam-like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate salts found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. The data then indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrix and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation-anion pairing in the salt but appears relatively independent of matrices tested, following normalization. Our results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.},
doi = {10.1002/2016JE005164},
journal = {Journal of Geophysical Research. Planets},
number = 4,
volume = 122,
place = {United States},
year = {Mon Apr 24 00:00:00 EDT 2017},
month = {Mon Apr 24 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 48 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Remote laser-induced breakdown spectroscopy (LIBS) for lunar exploration: REMOTE LIBS FOR LUNAR EXPLORATION
journal, January 2012

  • Lasue, J.; Wiens, R. C.; Clegg, S. M.
  • Journal of Geophysical Research: Planets, Vol. 117, Issue E1
  • DOI: 10.1029/2011JE003898

Detection of Perchlorate and the Soluble Chemistry of Martian Soil at the Phoenix Lander Site
journal, July 2009


Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars
journal, January 2017


Mineralogy of a Mudstone at Yellowknife Bay, Gale Crater, Mars
journal, December 2013


Hydrogen detection with ChemCam at Gale crater
journal, March 2015


Volatile and Organic Compositions of Sedimentary Rocks in Yellowknife Bay, Gale Crater, Mars
journal, December 2013


Sequence of infilling events in Gale Crater, Mars: Results from morphology, stratigraphy, and mineralogy: SEDIMENTARY INFILLING IN GALE CRATER
journal, December 2013

  • Deit, Laetitia Le; Hauber, Ernst; Fueten, Frank
  • Journal of Geophysical Research: Planets, Vol. 118, Issue 12
  • DOI: 10.1002/2012JE004322

Constraints on the origin and evolution of the layered mound in Gale Crater, Mars using Mars Reconnaissance Orbiter data
journal, August 2011


Sulfates in Martian Layered Terrains: The OMEGA/Mars Express View
journal, March 2005


Pre-flight calibration and initial data processing for the ChemCam laser-induced breakdown spectroscopy instrument on the Mars Science Laboratory rover
journal, April 2013

  • Wiens, R. C.; Maurice, S.; Lasue, J.
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 82
  • DOI: 10.1016/j.sab.2013.02.003

Sampling statistics and considerations for single-shot analysis using laser-induced breakdown spectroscopy
journal, April 2002


Mineralogy of the Martian Surface
journal, May 2014


Recalibration of the Mars Science Laboratory ChemCam instrument with an expanded geochemical database
journal, March 2017

  • Clegg, Samuel M.; Wiens, Roger C.; Anderson, Ryan
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 129
  • DOI: 10.1016/j.sab.2016.12.003

Hydration state of calcium sulfates in Gale crater, Mars: Identification of bassanite veins
journal, October 2016


Elemental analysis of halogens using molecular emission by laser-induced breakdown spectroscopy in air
journal, August 2014


Calcium sulfate veins characterized by ChemCam/Curiosity at Gale crater, Mars: CALCIUM SULFATE VEINS AT GALE CRATER
journal, September 2014

  • Nachon, M.; Clegg, S. M.; Mangold, N.
  • Journal of Geophysical Research: Planets, Vol. 119, Issue 9
  • DOI: 10.1002/2013JE004588

Handbook of Laser‐Induced Breakdown Spectroscopy
book, March 2013


Understanding the signature of rock coatings in laser-induced breakdown spectroscopy data
journal, March 2015


Effect of Laser-Induced Crater Depth in Laser-Induced Breakdown Spectroscopy Emission Features
journal, July 2005

  • Corsi, Michela; Cristoforetti, Gabriele; Hidalgo, Montserrat
  • Applied Spectroscopy, Vol. 59, Issue 7
  • DOI: 10.1366/0003702054411607

The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Science Objectives and Mast Unit Description
journal, July 2012


Volatile, Isotope, and Organic Analysis of Martian Fines with the Mars Curiosity Rover
journal, September 2013


Laser induced breakdown spectroscopy library for the Martian environment
journal, November 2011

  • Cousin, A.; Forni, O.; Maurice, S.
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 66, Issue 11-12
  • DOI: 10.1016/j.sab.2011.10.004

In situ calibration using univariate analyses based on the onboard ChemCam targets: first prediction of Martian rock and soil compositions
journal, September 2014

  • Fabre, C.; Cousin, A.; Wiens, R. C.
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 99
  • DOI: 10.1016/j.sab.2014.03.014

Paleoclimate of Mars as captured by the stratigraphic record in Gale Crater: STRATIGRAPHY OF GALE CRATER
journal, February 2010

  • Milliken, R. E.; Grotzinger, J. P.; Thomson, B. J.
  • Geophysical Research Letters, Vol. 37, Issue 4
  • DOI: 10.1029/2009GL041870

Strategies for Mars remote Laser-Induced Breakdown Spectroscopy analysis of sulfur in geological samples
journal, January 2011

  • Dyar, M. Darby; Tucker, Jonathan M.; Humphries, Seth
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 66, Issue 1
  • DOI: 10.1016/j.sab.2010.11.016

Calibrating the ChemCam laser-induced breakdown spectroscopy instrument for carbonate minerals on Mars
journal, January 2010

  • Lanza, Nina L.; Wiens, Roger C.; Clegg, Samuel M.
  • Applied Optics, Vol. 49, Issue 13
  • DOI: 10.1364/AO.49.00C211

The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Body Unit and Combined System Tests
journal, June 2012

  • Wiens, Roger C.; Maurice, Sylvestre; Barraclough, Bruce
  • Space Science Reviews, Vol. 170, Issue 1-4
  • DOI: 10.1007/s11214-012-9902-4

An integrated view of the chemistry and mineralogy of martian soils
journal, July 2005

  • Yen, Albert S.; Gellert, Ralf; Schröder, Christian
  • Nature, Vol. 436, Issue 7047
  • DOI: 10.1038/nature03637

Evidence for indigenous nitrogen in sedimentary and aeolian deposits from the Curiosity rover investigations at Gale crater, Mars
journal, March 2015

  • Stern, Jennifer C.; Sutter, Brad; Freissinet, Caroline
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 14
  • DOI: 10.1073/pnas.1420932112

First detection of fluorine on Mars: Implications for Gale Crater's geochemistry: First detection of fluorine on Mars
journal, February 2015

  • Forni, Olivier; Gaft, Michael; Toplis, Michael J.
  • Geophysical Research Letters, Vol. 42, Issue 4
  • DOI: 10.1002/2014GL062742

Optimization of laser-induced breakdown spectroscopy for rapid geochemical analysis
journal, October 2010


LMFIT: Non-Linear Least-Square Minimization and Curve-Fitting for Python
software, September 2014


Works referencing / citing this record:

Low‐level LIBS and Raman data fusion in the context of in situ Mars exploration
journal, June 2019

  • Rammelkamp, Kristin; Schröder, Susanne; Kubitza, Simon
  • Journal of Raman Spectroscopy, Vol. 51, Issue 9
  • DOI: 10.1002/jrs.5615

Effects of pulsed laser and plasma interaction on Fe, Ni, Ti, and their oxides for LIBS Raman analysis in extraterrestrial environments
journal, July 2019

  • Schröder, Susanne; Rammelkamp, Kristin; Hanke, Franziska
  • Journal of Raman Spectroscopy, Vol. 51, Issue 9
  • DOI: 10.1002/jrs.5650

An interval of high salinity in ancient Gale crater lake on Mars
journal, October 2019


Microwave-assisted laser induced breakdown molecular spectroscopy: quantitative chlorine detection
journal, January 2019

  • Wakil, M. A.; Alwahabi, Zeyad T.
  • Journal of Analytical Atomic Spectrometry, Vol. 34, Issue 9
  • DOI: 10.1039/c9ja00151d

A Two Components Approach for Long Range Remote Raman and Laser-Induced Breakdown (LIBS) Spectroscopy Using Low Laser Pulse Energy
journal, November 2018

  • Misra, Anupam K.; Acosta-Maeda, Tayro E.; Porter, John N.
  • Applied Spectroscopy, Vol. 73, Issue 3
  • DOI: 10.1177/0003702818812144

Shipboard Characterization of Tuvalu, Samoa, and Lau Dredge Samples Using Laser-Induced Breakdown Spectroscopy (LIBS)
journal, March 2019

  • Konter, Jasper G.; Finlayson, Valerie A.; Engel, Jacqueline
  • Applied Spectroscopy, Vol. 73, Issue 6
  • DOI: 10.1177/0003702819830793

Plasma Spectroscopy of Various Types of Gypsum: An Ideal Terrestrial Analogue
journal, July 2019

  • Rai, Abhishek K.; Pati, Jayanta K.; Parigger, Christian G.
  • Atoms, Vol. 7, Issue 3
  • DOI: 10.3390/atoms7030072

Plasma Spectroscopy of Various Types of Gypsum: An ideal Terrestrial Analogue
preprint, July 2019