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Effect of LIBS-Induced Alteration on Subsequent Raman Analysis of Iron Sulfides

Alsemgeest, Jitse and Pavlov, Sergey and Böttger, Ute and Weber, Iris (2022) Effect of LIBS-Induced Alteration on Subsequent Raman Analysis of Iron Sulfides. ACS Earth and Space Chemistry, 6 (9), pp. 2167-2179. American Chemical Society (ACS). doi: 10.1021/acsearthspacechem.2c00051. ISSN 2472-3452.

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Official URL: https://pubs.acs.org/doi/10.1021/acsearthspacechem.2c00051


Mineral alteration is a possible side effect of spectroscopic techniques involving laser ablation, such as laser-induced breakdown spectroscopy (LIBS), and is related to the interaction of the generated plasma and ablated material with samples, dust, or ambient atmosphere. Therefore, it is essential to understand these interactions for analytical techniques involving laser ablation, especially for space research. In this combined LIBS–Raman analytical study, pyrite (FeS_2) and pyrrhotite (Fe_{1–x}S) samples have been consecutively measured with LIBS and Raman spectroscopy, under three different atmospheric conditions: ∼10^{–4} mbar (atmosphereless body), ∼7 mbar, and Martian atmospheric composition (Martian surface conditions), and 1 bar and Martian atmospheric composition. Furthermore, a dust layer was simulated using ZnO powder in a separate test and applied to pyrite under Martian atmospheric conditions. In all cases, Raman spectra were obscured after the use of LIBS in the area of and around the formed crater. Additional Raman transitions were detected, associated with sulfur (pyrite, 7.0 mbar and 1.0 bar), polysulfides (all conditions), and magnetite (both minerals, 1.0 bar). Magnetite and polysulfides formed a thin film of up to 350–420 and 70–400 nm in the outer part of the LIBS crater, respectively. The ZnO-dust test led to the removal of the dust layer, with a similar alteration to the nondust pyrite test at 7.0 mbar. The tests indicate that recombination with the CO_2-rich atmosphere is significant at least for pressures from 1.0 bar and that plasma–dust interaction is insignificant. The formation of sulfur and polysulfides indicates fractionation and possible loss of volatile elements caused by the heat of the LIBS laser. This should be taken into account when interpreting combined LIBS–Raman analyses of minerals containing volatile elements on planetary surfaces.

Item URL in elib:https://elib.dlr.de/188489/
Document Type:Article
Title:Effect of LIBS-Induced Alteration on Subsequent Raman Analysis of Iron Sulfides
AuthorsInstitution or Email of AuthorsAuthor's ORCID iDORCID Put Code
Weber, IrisWestfälische Wilhelms-Universität MünsterUNSPECIFIEDUNSPECIFIED
Date:16 August 2022
Journal or Publication Title:ACS Earth and Space Chemistry
Refereed publication:Yes
Open Access:Yes
Gold Open Access:No
In ISI Web of Science:Yes
Page Range:pp. 2167-2179
Publisher:American Chemical Society (ACS)
Keywords:LIBS, Raman, alteration, iron sulfides
HGF - Research field:Aeronautics, Space and Transport
HGF - Program:Space
HGF - Program Themes:Space System Technology
DLR - Research area:Raumfahrt
DLR - Program:R SY - Space System Technology
DLR - Research theme (Project):R - Detectors for optical instruments
Location: Berlin-Adlershof
Institutes and Institutions:Institute of Optical Sensor Systems > Terahertz and Laser Spectroscopy
Deposited By: Pavlov, Dr. Sergey
Deposited On:27 Sep 2022 09:57
Last Modified:29 Nov 2023 14:52

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