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RAMAN STUDY OF SECONDARY MINERALS IN A RECENT LAVA TUBE

Conference Paper · June 2014

DOI: 10.13140/2.1.3413.1203

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11th International GeoRaman Conference (2014) http://dx.doi.org/10.13140/2.1.3413.1203

RAMAN STUDY OF SECONDARY ARY MINERALS IN A RECENT LAVA TUBE.

G. Guimbretière1†, A. Canizarès1, A. Finizola2, E. Delcher2, N. Raimboux1, E. Veron1, P. Simon1,B. Devouard3, A.
Bertil4
1
CNRS UPR3079 CEMHTI, Université d’Orléans, Orléans Cedex 2 - France, 2LGSR (UMR 7154), UR, IPGP, Saint
Denis de la Réunion, France,3Aix-Marseille
Marseille Université-CNRS-IRD
Université IRD (UM 34), CEREGE, Europôle de l’Arbois, Aix-
Aix
en-Provence, France,4Saint-Benoît,
Benoît, France,
† [email protected]
orleans.fr

Introduction:Extreme
Extreme conditions are all around
the world. From the atomic scale (where new technol- techno
ogical applications constrain more and more materials)
to the macroscopic scale (where environment
env is some-
times hostile for humans).In In this later case, risk
r man-
agement requiresobtaining quick and reliable informa-
tion on the physics and chemistry involved in these
hostile area that are volcanic eruption, nuclear accident
and so on.
Precisely, in the frame ofunderstanding and manage- manag
ment of volcanoes hazard, non on entirely
entire cooled post-
eruptive lava flow is a dynamic system with hot spots,
heat, fluid and ionic transfers.In
In this unstable and dan-
da
gerous environment, lava tubes act like natural drilling
allowing to probe inside the lava layer layers. Inside lava
tube one
ne can find secondary minerals resulting from
the physical and chemical activity inside the lava flow. Figure 1: Entrance of the lava tube (up right) Ex-
E
Thus, these secondary minerals are like undirect wi wit- emples of secondary minerals found in the lava tube
nesses of the chemical processes withinthe
within lava layer (left and bottom right)
and direct witnesses of the recent past of the enviro
environ-
ment in the lava tube. Experimental Methods:The
Methods: volcanic speleothem
These volcanic secondary minerals are seldomstudied was characterized at various length scales: the compo-
comp
[1,2] and a site of great interest is a recent lava tube sition, the morphology and the atomic
atomi structure were
from the 2007 eruption of the Piton de la Fournaise probed by mean of MEB-EDX, EDX, XRD and Raman spec-
spe
volcano (La Réunion island, Indian Ocean, France). troscopy. All these techniques were additionallyper-
This lava flow is more than 60 meters deep [3], still formed at CEMHTI laboratory after the field Raman
hoton some spots and presents varied fumarolic and campaign.Instruments
Instruments are ESEM XL40 (FEI), D8
secondary mineralsinside
inside lava tubes (Fig. 1). Advance diffractometer (BRUKER AXS), AXS) and for
The CEMHTI group (Orléans, France) has a great Raman, an InviaReflex Renishaw Spectrometer for the
experience of in situ Raman measurement
measurements and for the lab setup and a RA100 Renishaw spectrometer for the
study presented here, we adapted a laboratory in situ field setup. Figure 2 shows one of us (AC) working at
spectrometer [4,5]] for field measurements. the adjustment of the field Raman probehead.
In this paper, we present first the technical adapt
adapta-
tions made for a field use of the laboratory in situ spec-
trometer, its capabilities and limits as well.Secondly,
well.
wee present identification of secondary
second mineral phases
growing in the lava tube with a particular emphasis on
the study of whitespeleothems and dendrites by mean
of XRD, SEM-EDX and Raman spectroscopy.

11thGeoRaman International Conference, June 15-19,

19, 2014, St. Louis, Missourri, USA
 11th International GeoRaman Conference (2014) http://dx.doi.org/10.13140/2.1.3413.1203

Figure 2: Experimentalist at work in a lava

la tube with Thenardite (V)
the field Raman setup.

Preliminaryresults
esults and discussion:Figure
discussion 4
presents two typical uncorrected Raman spectra ac- 500 1000 1500 2000 2500 3000 3500 4000 4500

quired with the field setup from the white volcanic

speleothem shown on Figure
igure 3. Top spectrum is The-
Th

Raman Intensity (arb. units)

nardite (V) and bottom spectrum that of up to now
unidentified vanadate mineral. One immediately can
remark the presence of water with Thenardite, the
incredible flatness of the background and the narrow-
narro
ness of the main peaks: HWHM = 5 cm-1 (the resolu- Unidentified Vanadate Phase
tion of the spectrometer is ≈ 1 cm-11). All this elements
being the signatures of high crystalline quality probed
by mean of a high quality instrument.

200 400 600 800 1000 1200 1400

-1
Wavenumber (cm )
Figure 4 : Uncorrected Raman spectra acquired with the
field Raman setup.

Partial Conclusion: Three

hree months after the
t field
campaign on the volcano, the environmental conditions
condi
Figure 3 : White speleothem growing hanging to of the lava tube evolved very quickly and all the spe-
sp
the lava tube ceiling (top left). At right
righ are pictured leothems disappeared.
SEM imaging (top) and Ramancharacterization
characterization (bot-
tom) of it. Acknowledgement:The The authors warmly thank
theCNRS Interdisciplinary Mission
M for its support and
Among the minerogenetic mechanisms listed by the Grotte
rotte du Foulon team (Chateaudun, France) for
Fortiet al. [3] our study deals mainly with intermediate their help during the training of the field experiment.
experiment
temperature mechanisms isms (400 ÷ 0 °C) that are ions
exchange, substitution of atoms, supersa
upersaturation, depo- References:
sition
tion from aerosols and vapors, evaporation,
e oxida- [1] Forti P. (2005) Journal of Cave and Karst Stu-
tion/reduction and hydration/dehydration.
ehydration. The richness dies, 67, 3–13.
of processes is a nice reflection of the richness of in-
i [2] White W.B. (2010) Journal of Cave and Karst
formation about the physical-chemistry
chemistry dynamic of the Studies, 72, 75-85.
lava flow that should give such studies: Among others [3] Staudacher T. ett al., (2009) Journal of Volca-
classical secondary mineral phases, we observed the in nology
ogy and Geothermal Research, 184, 126-137.
situtransition
transition from sulfate hydrate (mirabilite)
( to the- [4] Guimbretière G. et al. (2013) Appl. Phys. Lett.,
nardite, the presence of various ous Na2SO4metastable 103, 041904.
phases and unidentified vanadates
anadates phases … [5] Canizarès A. et al. (2012) Journal of Raman
Spectroscopy, 43 1492–1497.
1497.

11thGeoRaman International Conference, June 15-19,

19, 2014, St. Louis, Missourri, USA

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