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Analysis of Minerals and Rocks by Laser-Induced

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Article in Spectroscopy Letters · September 2011

DOI: 10.1080/00387010.2011.573048

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Spectroscopy Letters, 44:399–411, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0038-7010 print=1532-2289 online
DOI: 10.1080/00387010.2011.573048
Analysis of Minerals and Rocks by
Laser-Induced Breakdown Spectroscopy
Diego M. Dı́az Pace1,2,
Norberto A. Gabriele3,
Mayra Garcimuño1,4,
Cristian A. D’Angelo1,4,
Graciela Bertuccelli1,2,
and Daniela Bertuccelli1,2
1 infrared Nd:YAG laser in open-path configuration. The emitted light in the
Instituto de Fı́sica ‘Arroyo Seco’,
Facultad de Ciencias Exactas,
U.N.C.P.B.A., Campus
Universitario, Paraje Arroyo Seco,
Tandil, Buenos Aires, Argentina
2
CONICET, Rivadavia, Buenos
Aires, Argentina
3
Facultad de Ciencias Exactas,
U.N.C.P.B.A., Campus
Universitario, Paraje Arroyo Seco,
Tandil, Buenos Aires, Argentina
4
CICPBA, La Plata, Buenos Aires,
Argentina
Received 8 February 2011;
accepted 14 March 2011.
Address correspondence to Diego M.
Dı́az Pace, Pinto 399, B7000GHG
Tandil, Buenos Aires, Argentina.
E-mail: ddiaz@exa.unicen.edu.ar
ABSTRACT Laser-induced breakdown spectroscopy (LIBS) technique was
applied for rapid analysis of major and minor elements composing geologi-
cal samples including minerals, rocks, and a soil sample. The plasma was
produced in air at atmospheric pressure by focusing on the targets a pulsed
UV-Vis was analyzed by a compact LIBS system to measure spectral emis-
sion lines of Si, Al, Fe, Ca, Na, K, Mg, C, Cu, Mn, and Ti. The experimental
issues relevant for the analysis of the different samples were investigated by
taking into account their peculiar features: drilling through a weathered
layer, roughness and grain-size considerations, statistical averaging, and
accuracy of the measurements. In this approach, the characterization of
the samples was achieved by studying the relative variations of the emission
intensities of each element normalized with respect to an internal standard.
The present study shows the usefulness of LIBS as a tool for reliable identi-
fication of field samples.
KEYWORDS laser-induced breakdown spectroscopy, LIBS, minerals, rocks
INTRODUCTION
Minerals and rocks that are found at a particular location contain impor-
tant clues about the geologic history of that site and how it originated and
has evolved with time. Field geology relies greatly on identification based
on a geologist’s assessment of certain physical properties and later classi-
fication at a laboratory facility, which is not always accurate. Due to its
advantages of lack of any sample preparation and in situ measurements,
Laser-Induced Breakdown Spectroscopy (LIBS) offers a tool for more-
reliable identification of field samples.
The aim of this work was to carry out a rapid analysis of major and minor
elements present in geological samples by LIBS technique. In this approach,
we employed a compact system equipped with a nonintensified detector
and without temporal resolution, and the results allowed the compositional
analysis of several minerals, rocks, and a soil sample. Furthermore, the LIBS
capability to drill through weathered layers on the sample surface to deter-
mine its composition as well as that of the underlying bulk composition
was addressed, and the experimental issues relevant for the analysis of
399
the different samples such as the accuracy of the
measurements, sample homogeneity, and grain size
were investigated.
LIBS Technique
LIBS is a very useful technique to survey, identify,
and quantify the chemical composition of a wide range
of samples in solid, liquid, or gaseous state by perform-
ing spectral analysis of the light emitted from a plasma
created on the target.[1] Thus, the resulting UV-Vis
emission spectrum contains characteristic lines from
the atoms, ions, and simple molecules present in the
plasma. LIBS possess several advantages compared
to other conventional techniques: (1) simple experi-
mental setup, (2) few or no sample preparation
needed, (3) in situ and stand-off analysis capabilities,
(4) microdestructiveness, (5) real-time measurement
of many elements simultaneously, and (6) depth profil-
ing and spatial resolution. These features allow LIBS to
perform measurements under conditions not feasible
with conventional analytical techniques (e.g.,
ETA-AAS, ICP-AES, and ICP-MS) that, supported by
the actual technology development in the compo-
nents, make it a very promising technique to be inte-
grated with the established atomic spectroscopic
methods.[2] Hence, it has been recently employed as
an analytical tool for field applications with the aim
of providing rock and soil analysis, as well as examin-
ation and characterization of archaeological find-
ings.[3–7] In the stand-off approach, direct remote
sensing, in which the laser and signal are transmitted
through a transparent atmosphere, is performed.[8]
The use of LIBS for material analysis is based on the fact
that all the elements are characterized by their distinc-
tive spectra. Thus, the elements present in the sample
are identified using their characteristic spectral lines.
Nevertheless, quantifying their concentration is a diffi-
cult task. The most common approach is using cali-
bration curves constructed with reference samples,
but these are not possible when dealing with unique,
complex, or a priori unknown samples (e.g., museum
pieces, archaeological findings). Moreover, the
ablation process depends on the target properties.[9,10]
In this direction, several methods for overcoming
matrix effects have been successfully employed, but
these are time-consuming.[11]
In the case of samples collected from the field, that
is, geological and archaeological fragments, LIBS
D. M. Dı´az Pace et al.
analysis is based on obtaining the overall compo-
sition through inspection of the target by producing
a small crater on its surface that is replicated at differ-
ent places, assuming that the plasma composition is
representative of that of the sample previous to the
laser ablation (stoichiometric ablation). Moreover,
natural materials usually present different degrees
of homogeneity, surface roughness, and grain size,
which affect the plasma formation, causing strong
shot-to-shot variations in the measured spectral
intensities.[12]
In addition, the use of LIBS for field analysis
imposes some constraints on size, weight, and
simplicity of the setup for placement on a rover or
rugged portable equipment in geological prospect-
ing.[13] Therefore, laboratory tests are of major impor-
tance for evaluating and optimizing the performance
of the technique with the goal of obtaining useful
analytical information under several environmental
conditions, such as at close or stand-off distances
and in atmospheres with different pressures and
compositions. Furthermore, a spectral library under
adequate conditions can be constructed in order to
analyze unknown samples by comparing the mea-
surements with reference spectra from a spectral
database.[15,16]
Several researchers have developed transportable
instruments to promote LIBS as an analytical tool in
the field. The first reported portable system was
made by Yamamoto et al.[17] who presented the
development of a portable instrument and its feasi-
bility for environmental monitoring. It consisted of
a small laser to generate the laser sparks and a
fiber-optic cable to collect the light, which was spec-
trally resolved with a compact spectrograph and
detected with an unintensified, nongated CCD. Pre-
liminary tests were successfully performed measur-
ing metals in soil, paint, and particles collected on
filters. In the work of Sallé et al.,[14] LIBS was evalu-
ated for qualitative analysis of different rock types
under Mars atmospheric conditions using a compact
experimental setup. Spectral lines from Ca, Mg, Fe,
and Si were detected in basalt and dolomite in the
225–320 spectral range, without gating the detection
system, and using a nonintensified detector. The
results were compared with spectra recorded from
samples constructed with rock powder standards.
In the paper of Palanco et al.,[13] the design and con-
struction considerations of field-deployable LIBS
400
equipment provided with an intensified CCD detec-
tor with time resolution for remote elemental sensing
were reported. Moreover, the main parameters influ-
encing its performance at stand-off distances were
studied. Harmon et al.[12] reported the development
of a prototype LIBS system as a real-time man-
portable geochemical sensor. Time-resolved broad-
band spectra in the region 200–980 nm under normal
atmospheric conditions were acquired from soil,
minerals, and metal samples. Results were encour-
aging for the use of this prototype in geochemical,
mineralogical, and environmental applications. An
example of the application of LIBS to provide online,
real-time analyses was reported by Gaft et al.,[18] who
developed an industrial LIBS machine based on a
small and robust CCD spectrometer with time resol-
ution, which was successfully tested for quantifying
minerals in raw ores and main ash-forming elements
in coal. Due to technology development, modern
and compact LIBS instruments have become com-
mercially available in the market,[19,20] in which
the use of low-cost nongated detection systems
have proved very good performance for specific
applications.[21–23]
Minerals and Rocks
Minerals are naturally occurring solids with an
organized crystalline structure composed of either a
single chemical element or a compound, and they
are the fundamental constituents of rocks and soils.
They can be accurately identified by both X-ray
and chemical analysis that reveal their structure and
chemical composition, which are the ‘‘fingerprints’’
of a mineral. Nevertheless, these tests require
expensive equipments, are time-consuming, and
often destroy the specimen. In practice, since struc-
ture and composition affect certain physical proper-
ties of minerals, geologist use a number of criteria
such as shape, hardness, and color to identify miner-
als in the field. But these features usually do not
necessarily lead to the correct recognition of any
unknown material. On Earth exist thousands of dif-
ferent mineral species, which are classified according
to their chemistry into the following classes: native
elements, sulfides, halides, oxides, carbonates, sul-
fates, phosphates, silicates, and mineraloids. More-
over, each class is further divided into several
subclasses by their structures, and each subclass
401
may too contain different groups of minerals with
very similar characteristics.
Mineral compositions are more complex than their
chemical formulas indicate and are heterogeneous
within them. Hence, their compositions vary by sub-
stitution of one or more of its elements by another
atom that takes its place in the crystalline framework,
for example the isomorphic series.[24]
A rock is a solid part of the Earth’s crust that is gen-
erally composed of more than one mineral. Then,
rocks cannot be classified in the same way as can
minerals because they may contain an inhomoge-
neous mixture of minerals in the form of grains. Geol-
ogists classify rocks according to how they were
created: Igneous rocks, which are further divided into
intrusive or plutonic rocks and extrusive or volcanic
rocks; sedimentary rocks; and metamorphic rocks.
MATERIALS AND METHODS
Experimental Setup
The setup used to analyze the samples in the lab-
oratory is shown in Fig. 1. A Q-switched Nd:YAG
pulsed laser (Laser Big Sky, Model ultra, Laser Tech-
nologies, Inc., USA) operating at the fundamental
wavelength 1064 nm, at a repetition frequency of
2 Hz and with a pulse width of 5–7 ns and an energy
of 50 mJ was used to produce the plasma. The sam-
ples were placed on a translator stage allowing the
displacement in a plane normal to the incidence
direction in order to control the position of the sam-
pling point and obtain spatially resolved measure-
ments. The laser pulses were focused with a quartz
lens (L1) of 200-mm focal length onto the sample sur-
face. The plasma light was collected at a right angle
with respect to the laser beam and focused with a
second quartz lens (L2) of 100-mm focal length onto
the entrance slit (100-mm width) of a small mono-
chromator (Model 504, Acton Research Corporation,
USA) of 50-cm focal length, provided with a
1200-grooves=mm diffraction grating and spectral
coverage over the 200–1000-nm range, over which
all elements have emission lines. In contrast with
the gated, intensified CCD cameras usually used for
LIBS experiments, light detection was performed by
a nonintensified nongated linear photodiode array
detector (Model RY-1024, PDA, Princeton Instru-
ments, Inc., USA) covering a spectral window of
Analysis of Minerals
FIGURE 1 Experimental setup and observation geometry.

TABLE 1 Mineral Samples Analyzed

Mineral samples Class Subclass Group Formula Characteristics
Purchased gems
Quartz (Rock crystal) Silicate Tectosilicate — SiO2 Quartz crystal, prismatic,
pyramidal, hyaline,
without visible impurities.
Magnesite Carbonate — — MgCO3 Polished, cryptocrystalline,
milky white, hardness 6.
No chemical reaction
occurred with HCl.
Manganite –Calcite Carbonate — — [Mn,Ca]CO3 Polished, milky white,
semitranslucent, hardness
5. Chemical reaction
occurred with HCl.
Tourmaline Silicate Cyclosilicate Tourmalines (Na,Ca)(Mg,Al)6- Polished, black, crystalline,
[B3Al3Si6(O.OH)30 hardness >7. Chemical
formula corresponding to
the most common species.

Gems collected from the field

Quartz Silicate Tectosilicate — SiO2 Cloudy, prismatic, pyramidal
crystals and with a
superficial coating of
reddish–gray clusters.
Biotite Silicate Phyllosilicate Micas K(Mg,Fe)3AlSi3O10(F,OH)2 Translucent, metallic gray,
forming a thick-grained
association with quartz.
Microcline Silicate Tectosilicate Feldspars KAlSi3O8 Crystalline, pale pink, good
cleavage, with albite
lamella pertite, small
clusters (<1 mm in size) of
white mica (muscovite)
and quartz.
Malachite Carbonate — — CuCO3  Cu(OH)2 Green, soft bright, long
radial fibers, hardness <5,
and pale green streak.

D. M. Dı´az Pace et al. 402

50 nm. The PDA was triggered at the start of the laser
pulse in such a way that it recorded the plasma emis-
sion during its entire lifetime. A computer was used
for data acquisition from the detection system.
The experimental arrangement was in an open-
path framework in which the laser beam and the
plasma light are transmitted through the air atmos-
phere. This configuration was chosen for its sim-
plicity and versatility, which make feasible many
applications. In fact, the analysis of environmental
and geological targets in the field and remote sensing
at real-time (open-path, stand-off LIBS) under
reduced air pressure or simulated extraterrestrial
atmosphere are envisaged.
Samples
LIBS analyses were accomplished on different
mineral and rock samples, which were classified into
three different groups. The first was composed by
purchased mineral gems: quartz (rock crystal), mag-
nesite, manganite–calcite, and tourmaline (Table 1).
The second group was composed by minerals col-
lected from the field: biotite, microcline, quartz,
and malachite (Table 1). The third group was formed
by collected rocks: caliche, tonalite, and basalt.
Moreover, a soil sample (loess) was investigated
(Table 2). All the samples were previously examined
through a megascopic analysis to determine their
characteristics (shown in Table 1 and Table 2) and
address the subsequent LIBS analysis. The samples
collected from the field were analyzed in their natu-
ral state and without any previous treatment.
TABLE 2 Rock Samples Analyzed
Rock samples Classification
Tonalite Igneous. Intrusive. Plagioclase, hornblende,
biotite, quartz, opaque
minerals.
Basalt Igneous. Volcanic. Microcrystalline minerals, glass.
Caliche Sedimentary. Chemical. Calcite, quartz. Silts.
Loess Sedimentary. Eolian. Quartz, k-feldspar, plagioclase,
mica, hornblende.
403
RESULTS AND DISCUSSION
The major and minor components of the samples
were analyzed by measuring line emission intensities
from Si, Al, Fe, Ca, Na, Mg, and K, which form
the Earth’s crust; and other elements of interest to
geologist, such as Mn, Ti, Cu, and C. Since
time-integrated spectra contain contributions from
elemental emission lines and the plasma continuum
emission, the signal-to-noise ratio was improved by
accumulation of many spectra on each sampling
point on the target surface. The compositional analy-
sis was carried out by measuring the relative varia-
tions of line emission intensities from the analytes
between the different samples, selecting several
emission lines to represent the corresponding
elemental concentration for each element.
Analysis of Minerals
In gem samples, spectra were recorded by
accumulation of 20 consecutive laser sparks deliv-
ered in one arbitrary point of the surface. Even
though their compositions are expressed in a simple
manner in Table 1, minerals are inhomogeneous in
detail because of the large amount of ionic substi-
tution, which originates a natural compositional vari-
ation on a micron spatial scale. Thus, in the case of
natural minerals, the spectra were obtained by aver-
aging measurements accumulated from firing the
samples on five different surface locations. On each
location, the signal was integrated over 20 laser shots
at the same point to obtain the bulk composition
Minerals Characteristics
Rough surface, crystalline,
medium-sized grains, gray.
Foliate, affected by
metamorphism.
Hard, dense, dark gray,
aphanitic crystalline with
glassy appearance and
vesicles.
Earthy white, fined grains,
moderate consolidation,
chemical reaction occurred
with HCl.
Friable, pale yellow (dried),
soft.
Analysis of Minerals
after 30 previous cleaning shots to remove weath-
ered layers or any possible artifact due to handling
the samples at the laboratory.
Typical examples of the spectra measured from
minerals, with the most intense lines identified, are
shown in Fig. 2, Fig. 3, and Fig. 4. In Fig. 2a, it can
be seen that a strong Si transition, a spectral signature
of silicates, is present in quartz, manganite–calcite,
and tourmaline. Moreover, Al and Si lines character-
istic of aluminosilicates were detected in tourmaline,
and several Fe and Mg lines were observed in both
tourmaline and manganite–calcite. In Fig. 2b, lines
of Si, Ca, and Fe were identified in tourmaline and
manganite–calcite. In this region, Si emissions are
weaker, while those from Mg and Fe remain unre-
solved. In addition, strong Ca lines were recognized
in manganite–calcite, and strong Al lines were recog-
nized in tourmaline. In Fig. 2c, the well-known
doublet of Na was detected in tourmaline and
manganite–calcite. In Fig. 2d, lines corresponding
to K were observed in tourmaline and manganite–
calcite, as well as other lines of Si and Mg. In the
manganite–calcite sample, in addition to Ca and
FIGURE 2 Detected lines of the major elements of Earth’s crust in mineral samples of Table 1. Some spectra were shifted vertically for clarity.
D. M. Dı´az Pace et al.
Mn, the presence of emission lines of other elements
was detected. We speculated that this sample is
probably a solid solution of several elements (Fe
and Mg) and has some impurities of quartz and K
feldspar (Si, Al, Na, and K). The detection of Fe in
tourmaline confirms, in agreement with its dark
tonality, that it corresponds to the Fe-rich variety
called ‘‘schorl.’’ In Fig. 3, it is shown that spectra from
biotite contain Si, Al, K, Mg, and Fe. Moreover,
microcline exhibited lines of Si, Al, Ca, Na, and K.
The measurements on malachite allowed us to
determine the presence of Mg, Ca, Si, and Fe, as well
as K. Additionally, Mn was detected in manga-
nocalcite, Ti and Cu were found in malachite,
and C was in both of them and also in magnesite
(Fig. 4).
In plasma produced by the interaction of the laser
with a solid target in air, the surrounding atmosphere
near the plume is excited, allowing the detection of
its major constituents. Moreover, hydrogen emission
is expected because of the water vapor due to the
natural humidity of the atmosphere.[25–27] In our
experiment, emission atomic lines of N, O, and H
404
FIGURE 3 Elements detected in minerals microcline, biotite, and malachite collected from the field.
were detected. O and H lines are the result of contri-
butions of both the sample and the ambient air, and
they should be analyzed at a reduced pressure to
minimize the contribution of the atmosphere to line
intensities in order to estimate their concentration
in the sample.[8] On the other hand, N lines origi-
nated only from the air, since the samples do not
contain any nitrogen at all.
Drilling Through Weathered Layers
The natural quartz fragment presented a super-
ficial coating that needed to be passed over and that
needed its character to be determined. The cleaning
process was monitored by collecting the plasma
emission layer by layer. Figure 5a shows the spectral
measurements as the coating is drilled by repetitive
sampling at the same spot, where emission lines of
Fe, Mg, and Si were identified. The changes in Mg
and Fe line intensities with respect to that of Si
are shown in Fig. 5b. When the emissions of the first
elements stopped decreasing and the emission of the
latter element stopped increasing, the cleaning pro-
cess was complete. It can be seen that a superficial
405
layer of MgOx and FeOx was completely removed
after 30 laser shots, and then the presence of Si
was detected clearly.
Issues Affecting the Accuracy
of LIBS Analysis
The characteristics of plasmas generated on the
surface of solid samples depend in a complicated
way on the experimental conditions, including the
features of the material being analyzed, the laser
parameters, and the detection system. Thus, the
reliability of the analytical results was studied
through the different issues affecting the accuracy
of LIBS measurements.
In our experiment, variations in the measured line
intensities were observed as a result of (1) the sample
features, (2) fluctuations intrinsic to LIBS method, and
(3) the instrumental noise. The sample characteristics
affect the accuracy of the results through systematic
errors caused by matrix effects, surface roughness,
grain size, and compositional inhomogeneities. More-
over, laser energy fluctuations, focusing length, and
Analysis of Minerals
FIGURE 4 Detected lines of C, Mn, Ti, and Cu in manganite–
calcite, magnesite, and malachite.
the region of the plasma plume imaged onto the
entrance slit of the monochromator, which is
spatially inhomogeneous, cause both random and
systematic variations related to the reproducibility of
the method under different conditions of mea-
surement. Additionally, the dark current and the pho-
ton noise originate random intensity fluctuations
independent of the source that affect the instrumental
repeatability under the same conditions of measure-
ment.
In order to minimize the systematic errors, thereby
increasing the accuracy, and to evaluate the contri-
bution of each source of random errors (precision
given by the relative standard deviation [RSD] of suc-
cessive measurements) in the measurements, the fol-
lowing analysis was carried out: Samples providing a
plane side (i.e., polished gems, biotite) were exam-
ined to minimize changes in the signal originated
by laser defocusing due to either surface roughness
or repositioning of them on the sample stage. In
addition, the central zone of the plasma was imaged
D. M. Dı´az Pace et al.
FIGURE 5 (a) Depth profiling of the quartz sample collected
from the field through a weathered coating of MgOx and FeOx oxi-
des; (b) Peak-intensity ratios of Mg and Fe lines with respect to Si
as a function of the laser shot number.
on the entrance slit of the monochromator, keeping
fixed the focusing length, in such a way that the
detected signal was optimized. As an example,
shot-to-shot variations in line intensities of Fe, Mg,
Al, and Si were observed in one-shot spectra from
biotite, acquired under the aforementioned pro-
cedure. The accumulated spectra had averaged peak
intensities with an RSD  10% for all the lines mea-
sured. These variations arose mainly from the instru-
mental noise and laser energy fluctuations, being
independent of the analyte. The experimental peak
intensities of the lines measured (previously cor-
rected by the quantum efficiency of the detector
and by background subtraction) were normalized
with respect to the N peak emission line at
744.23 nm to compensate for energy variations. N
was selected as an internal standard because it is
the most abundant element present in the air ambi-
ent, and it is generally not present in minerals and
406
rocks. The stronger N line at 746 nm was discarded
because it is affected by interference of close Ca
lines. We observed that the normalized ratios had
an improved RSD <5% corresponding only to the
instrumental repeatability. Therefore, despite signifi-
cant shot-to-shot variations in the emission intensity
of the plasma, the line intensity ratios had good accu-
racy (5%) for compositional analyses just integrat-
ing several laser shots.

Analysis of Rocks
Rocks are intrinsically inhomogeneous since they
are a mixture of different particles of minerals.
Consequently, they usually present several degrees
of surface texture and=or grain size, which should
be considered in the analysis. Most rocks are formed
up by grains of minerals larger than 1 mm and up to
some centimeters in size. The mineral grains may be
large enough to be easily identified (e.g., tonalite),
barely distinctive grains (e.g., basalt), or microscopic
grains (e.g., slate). This gives rise to some concerns
since the crater originated by the focused laser spot
onto the sample surface is typically on the order of
100 mm to 1 mm wide and 10–20 mm deep, depend-
ing on the irradiance and the properties of the target. FIGURE 6 Spectra obtained from tonalite at different sampling
Therefore, measurements representative of only one positions.

mineral or perhaps of the interface between two

minerals could be obtained. Thus, the issues of inho-
mogeneity and grain size were considered in carry-
ing out a grid of measurements consisting in a set
of sampling points regularly distributed over an area
with such a size and spacing depending on the grain
size. The emission of the plasmas at each point of the
grid was accumulated to produce each spectrum.
In this approach, two samples of igneous rocks,
tonalite and basalt, and one sample of sedimentary
rock, caliche, were analyzed as examples of rocks
that could be commonly found in the field
(Table 2). Additionally, a loess sample in the form
of a pressed pellet was inspected to assess LIBS for
potential environmental applications.
Tonalite was the most heterogeneous sample in
our work. It presented easily seen coarse mineral
grains >1 mm in size and a considerably rough sur-
face. A grid of measurements was carried out with
a total of 25 sampling points, arranged in five rows
by five columns with 1-mm spacing between them.
An example of the spectra recorded from several grid
points of tonalite is shown in Fig. 6. It can be seen
that different emission lines with different intensities
are present at different positions on the surface. This
is clearly reflected in the statistics computed from the
grid with the experimental peak-intensity ratios of
the available lines (Table 3). The high RSD (70%)
is a joint consequence of mineral grains and surface
roughness (originating laser defocusing). For the
purpose of this work, it was a good approximation
considering the sampling area (16 mm2) as rep-
resentative of the overall features and the chemical
composition of this kind of sample.
On the other hand, basalt was a fine-grained frag-
ment with a high degree of surface roughness. Spec-
tra were averaged over five replicates at different
random positions of the sample surface. The statistics
of the peak-intensity ratios are shown in Table 4. The
RSD was approximately 15%, as a result of the
combination of fluctuations due to laser energy
and roughness, while the grain-size effects were
negligible.

407 Analysis of Minerals

TABLE 3 Statistics of Line Peak-Intensity Ratios from Tonalite
in a Grid of Measurements

Peak-Intensity
ratio Min Max Range Mean RSD (%)
Fe=N I275.01=I744.23 0 2.9 2.9 1.6 70.7
Mg=N I279.55=I744.23 0 7.0 7.0 3.6 72.6
I280.27=I744.23 0 5.8 5.8 3.0 71.0
I285.21=I744.23 0 2.8 2.8 1.6 62.2
Si=N I285.21=I744.23 1.6 2.6 1.0 2.0 15.2
Al=N I307.47=I744.23 2.2 9.1 6.9 5.9 43.7
I308.85=I744.23 1.1 4.8 3.7 3.3 36.4
Ca=N I393.37=I744.23 0.6 4.2 3.6 1.6 53.5
I396.85=I744.23 0.7 3.1 2.4 1.2 50.2
Na=N I589.00=I744.23 0.8 5.9 5.1 3.5 49.4
I589.60=I744.23 0.8 4.6 3.8 2.8 45.2
K=N I766.49=I744.23 0.7 4.6 3.8 1.8 61.5
I768.90=I744.23 0.8 3.5 2.8 1.4 54.4

Tonalite and basalt are both igneous rocks with an

analogous elemental composition where the charac-
teristic spectral lines of the elements forming the
minerals quartz, mica, feldspar, and ferromagnesian
mineral were recognized. Like basalt, caliche and
loess were also fine-grained samples with moderate
consolidation. No significant fluctuations were
observed in this case, so measurements from both
FIGURE 7 Some spectra obtained from (a) caliche; and (b)
samples were not affected by roughness. Examples loess.
of spectra from caliche and soil are shown in Fig. 7a
and Fig. 7b, respectively. It is observed that Ca lines
are dominant in the spectrum of caliche, and strong Sample Characterization
Ti lines were detected in loess. Figure 8 depicts the results obtained in this work
from the analysis of several collected minerals, rocks,
and a soil sample. The analysis was based on com-
TABLE 4 Statistics of Line Peak-Intensity Ratios from Basalt in puting the ratios of the peak intensities of the most
Different Positions intense emission lines characteristic of each element
Peak-Intensity with respect to an internal standard (i.e., N). Differ-
ratio Min Max Range M RSD (%) ent lines of the same analyte having different intensi-
Fe=N I275.01=I744.23 2.6 3.1 0.5 2.9 7.8 ties but a similar qualitative behavior were averaged
Mg=N I279.55=I744.23 3.5 4.7 1.2 4.1 11.8 to give just one representative result for each sample.
I280.27=I744.23 3.0 4.0 0.9 3.4 10.8 In addition, it should be stressed that the results
I285.21=I744.23 1.7 2.2 0.4 1.9 9.3 belonging to different samples cannot be compared
Si=N I285.21=I744.23 1.9 2.4 0.5 2.2 9.9
in between because of matrix effects. For that reason,
Al=N I307.47=I744.23 2.8 3.5 0.7 3.3 8.9
I308.85=I744.23 3.3 4.4 1.0 4.1 10.7
the following analysis is based on the relative varia-
Ca=N I393.37=I744.23 3.7 5.5 1.8 5.0 15.0 tions of the intensity ratios of the elements of interest
I396.85=I744.23 3.1 4.4 1.3 4.0 13.0 observed in the different samples.
Na=N I589.00=I744.23 4.7 5.7 1.0 5.1 8.2 The major components of biotite are Si, Al, and
I589.60=I744.23 4.3 5.0 0.7 4.7 5.6 Mg, while Fe, K, and Na are also present but at minor
K=N I766.49=I744.23 1.7 2.4 0.6 2.0 12.8
quantities. The presence of Si and Al indicates that
I768.90=I744.23 1.5 2.0 0.4 1.7 11.3
this mineral is an aluminum silicate, while K, Mg,

D. M. Dı´az Pace et al. 408

FIGURE 8 Averaged peak-intensity ratios obtained for minerals and rocks collected from the field. In the case of tonalite, the maximum
and minimum values are shown. The error bars correspond to the standard deviations.
and Fe complete their elemental composition. In
addition, a little quantity of K is replaced by Na.
Microcline contains Al, Si, and Na as major element
constituents, together with K and Ca, corresponding
to a variety of K feldspar (or alkaline feldspar) usually
found in pegmatite rocks, from which the sample
seems to come. It is an aluminum silicate with a sig-
nificant amount of Na because the mineral was
sampled transversely to perthite lamellae, a structure
of layers of the mineral albite (Na-plagioclase) that
is the Na-rich end of the Ca-Na feldspar series. At
lower temperatures, the K feldspars separate the Na,
which crystallizes with AlSi3O8, forming, in this case,
layers of albite inside the K-feldspar crystal, in a
process called ‘‘exsolution.’’ Moreover, it frequently
contains some amount of Ca since it is also a solid sol-
ution of the plagioclase feldspar series.
Malachite is a secondary mineral formed typically
in the superficial oxidation zones of copper ore
409
deposits by weathering processes affecting cal-
careous rocks containing copper sulfurs. The sample
analyzed is impure. We speculate that, in addition to
Cu (not shown in Fig. 8), it contains significant
amounts of Si and Ca probably because they are often
found together with the mineral in the ganga.[28,29] Fe
could be due to limonite, which is formed in the
upper part of the oxidation zone (gossan), and which
forms a thin film that covers the malachite. Addition-
ally, it is presumed that Mg, Na, and K were detected
as impurities of the adjacent wall rock.
Quartz sample collected from the field is a good
example of how LIBS can perform a depth-profiling
analysis (Fig. 5). The Si emission line, which was
hidden and hardly identified, could be detected cleanly
after a coating of Fe and Mg oxides was identified and
removed to obtain the underlying bulk composition.
The results obtained from basalt suggest a nearly
uniform distribution of its chemical constituents,
Analysis of Minerals
indicating a fine-grained volcanic rock where the
spectra recorded from each sampling spot involve
several minerals of microscopic size. The strong pres-
ence of Na, Ca, and Al, together with Si, indicates that
the plagioclase of this igneous rock has a near inter-
mediate composition (andesine–labradorite) that
defines an andesitic–basaltic rock; the other chemical
elements (Mg, Fe) are usually present in ferromagne-
sian minerals (pyroxenes, amphiboles) formed at
higher temperatures, and K belongs to an amphibole.
The spectra recorded from tonalite shows a het-
erogeneous distribution of the different chemical ele-
ments. Fe and Mg, constituents of biotite and
hornblende, are not detected in some positions of
the grid, as shown in Fig. 6, indicating a grainy rock
where the felsic minerals (plagioclase, K feldspar,
quartz) have a grain size greater that the laser spot.
Moreover, the larger amount of Na with respect to
Ca indicates that the sample is an acid plagioclase,
K is due to an alkali feldspar, and the lack of Si seems
to show that the rock is close to diorite.
The loess sample has the typical elements of
igneous rocks. In fact, the mineral components char-
acteristics of the Argentine pampean loess are andes-
itic plagioclases, quartz, orthoclase, volcanic glass
shards, altered feldspars, volcanic rock fragments,
organic opal, iron ores (magnetite, hematite, ilmenite,
etc.), illite, amphiboles, and pyroxenes.[30,33] The pam-
pean loess is formed by eolic silts from the Tertiary and
Quaternary Ages. These sediments came from dry
areas at the Patagonia and the Andes Range mixed
with volcanic ash from the Andean Arc, which had a
major role in the formation of loess. It suffered a sub-
sequent fluvial transformation, giving rise to loessoid
mud sediments. Additionally, Ti (not shown in Fig. 8)
comes from the titaniferous-variety magnetite.[30–33]
Large amounts of Ca and Mg were detected in
caliche, locally called ‘‘tosca,’’ because it is a carbonate
concretion developed in the pampean loess by adding
grains from its supporting material. In addition, the
elements of loess are found as impurities.
CONCLUSIONS
The analysis of geological samples was carried out
by using a compact, laboratory-based LIBS system in
open-path configuration equipped with a noninten-
sified, nongated detector. The samples analyzed
were purchased gems, minerals, and rock fragments
D. M. Dı´az Pace et al.
collected from the field and a soil sample in the form
of a pressed pellet. We measured spectral lines
characteristic of the major components of the Earth’s
crust including Si, Al, Fe, Ca, Na, K, and Mg and lines
from other elements of interest, that is, C, Cu, Mn,
and Ti, and from the atmoshere, that is, N, O, and H.
The LIBS capability to drill through a weathered
layer allowed determining the character of the oxides
covering superficially a quartz fragment as well as its
bulk composition. The influence of the samples’ fea-
tures, such as roughness, and the accuracy of the mea-
surements were also investigated. Thus, in natural
minerals the spectra were averaged over different loca-
tions to determine their composition, and in rocks their
intrinsic characteristics of inhomogeneity and=or grain
size were taken into account by carrying out a grid of
measurements to obtain the overall composition. After
that, an internal standard normalization with respect to
a proper N emission line was carried out to compen-
sate laser energy variations. Since matrix effects pre-
vent the comparison of absolute intensity ratios, a
compositional analysis was performed by studying
the relative variations of line emission ratios of the
chemical elements between the different samples.
The results obtained allowed the characterization of
the samples and illustrated the importance of some
relevant experimental issues for LIBS geochemical
applications. Nevertheless, the LIBS measurements
presented provide a basis for discrimination of some
but not all of the samples. The discrimination can be
improved using different experimental conditions or
spectral analysis techniques, such as statistical multi-
variate analyses. Moreover, stricter research of the
issues of line sensitivity, matrix effects, ionization
degree of the elements in the plasma, and self-
absorption should be accomplished in order to achieve
a semiquantitative or quantitative analytical determi-
nation. In this case, the compositions obtained by LIBS
should be compared to those obtained by other stan-
dard techniques such as X-Ray Fluorescence (XRF),
inductively coupled plasma-atomic emission spec-
trometry (ICP-AES), and inductively coupled plasma-
mass spectrometry (ICP-MS).
ACKNOWLEDGMENTS
The authors thank Dr H. F. Ranea Sandoval and M.
Giaconi for their valuable suggestions about this
work.
410
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411 Analysis of Minerals