Spectrochimica Acta Part B 62 (2007) 739 – 768

www.elsevier.com/locate/sab

Review
Laser-Induced Breakdown Spectroscopy in open-path configuration
for the analysis of distant objects
B. Sallé a,⁎, P. Mauchien b , S. Maurice c
a
Noveltis, Parc Technologique du Canal, 2 avenue de l'Europe, 31520 Ramonville Saint Agne, France
b
CEA Saclay, DEN/DPC/SCP, Bât.467, 91191 Gif sur Yvette Cedex, France
c
Observatoire Midi-Pyrénées, Centre d'Etude Spatiale des Rayonnements, 9 avenue du Colonel Roche, BP 4346, 31028 Toulouse Cedex 04, France
Received 27 April 2007; accepted 2 July 2007
Available online 10 July 2007

Abstract

A review of recent results on stand-off Laser-Induced Breakdown Spectroscopy (LIBS) analysis and applications is presented. Stand-off LIBS
was suggested for elemental analysis of materials located in environments where any physical access was not possible but optical access could be
envisaged. This review only refers to the use of the open-path LIBS configuration in which the laser beam and the returning plasma light are
transmitted through the atmosphere. It does not present the results obtained with a transportation of the laser pulses to the target through an optical
fiber. Open-path stand-off LIBS has mainly been used with nanosecond laser pulses for solid sample analysis at distances of tens of meters. Liquid
samples have also been analyzed at distances of a few meters. The distances achievable depend on many parameters including the laser
characteristics (pulse energy and power, beam divergence, spatial profile) and the optical system used to focus the pulses at a distance. A large
variety of laser focusing systems have been employed for stand-off analysis comprising refracting or reflecting telescope. Efficient collection of
the plasma light is also needed to obtain analytically useful signals. For stand-off LIBS analysis, a lens or a mirror is required to increase the solid
angle over which the plasma light can be collected. The light collection device can be either at an angle from the laser beam path or collinear with
the optical axis of the system used to focus the laser pulses on the target surface. These different configurations have been used depending on the
application such as rapid sorting of metal samples, identification of material in nuclear industry, process control and monitoring in metallurgical
industry, applications in future planetary missions, detection of environmental contamination or cleaning of objects of cultural heritage. Recent
stand-off analyses of metal samples have been reported using femtosecond laser pulses to extend LIBS capabilities to very long distances. The
high-power densities achievable with these laser pulses can also induce self-guided filaments in the atmosphere which produce LIBS excitation of
a sample. The first results obtained with remote filament-induced breakdown spectroscopy predict sample analysis at kilometer ranges.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Laser-Induced Breakdown Spectroscopy; LIBS; Stand-off analysis

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740
2. LIBS fundamentals for the design of a stand-off instrument . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
3. Stand-off LIBS analysis with nanosecond pulses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
3.1. Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
3.1.1. Laser systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
3.1.2. Optical systems for laser focusing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
3.1.3. Optical systems for plasma light collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748
3.1.4. Spectrograph and detection systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750

⁎ Corresponding author.
E-mail address: beatrice.salle@voila.fr (B. Sallé).

0584-8547/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2007.07.001
740 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768

3.2. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750

3.2.1. Industrial applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750
3.2.2. Detection of contamination in insulator systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754
3.2.3. Environmental control. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754
3.2.4. Planetary exploration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754
3.2.5. Detection of explosive residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
3.2.6. Cleaning of objects of cultural heritage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
3.2.7. Stand-off analysis of liquid samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
4. Stand-off LIBS analysis with femtosecond pulses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
4.1. Remote analysis by conventional LIBS using femtosecond laser pulses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
4.2. Remote analysis by filament-induced breakdown spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
5. Synthesis of stand-off LIBS performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765
6. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766

1. Introduction Stand-off LIBS analysis requires generating analytically

Since 1963, where was published the first analytical use of a
laser plasma for spectrochemical analysis of surfaces [1], the
Laser-Induced Breakdown Spectroscopy (LIBS) technique has
demonstrated its potential in qualitative analysis and quantita-
tive determination of elemental composition of solids even in
hostile environments, liquids, gases, aerosols and, environmen-
tal and geological samples. The analytical interest of LIBS is its
multi-element capability, its applicability to all sample types, its
low sample requirements, its lack of sample preparation and its
speed of acquisition allowing real-time measurements. One of
the unique capabilities of LIBS is to perform remote measure-
ments in field environments where the sample may be many
meters from the instrumentation. In his review on laser remote
sensing published in 1998, Panne classified LIBS as an indirect
remote-sensing technique [2]. He distinguished indirect remote
sensing, in which the laser or the signal is brought through fiber
optics or other means into contact or near the target from direct
remote sensing in which both the laser and signal are used along
an open atmospheric path. Remote LIBS can indeed be
implemented by transporting the laser pulses to the target
through a fiber optic and by collecting the plasma light and
transporting back to the detection system using either the same
optical fiber or a second fiber optic cable. This method which
has been demonstrated over distances up to 100 m requires that
the optical fiber be positioned adjacent to the sample. Therefore,
the use of fiber optic is of restricted application and even
impossible in cases where contaminated or aggressive chemical
or temperature environments may affect the probe, or when
large areas must be analyzed. In these cases, an open-path
configuration is used in which the laser beam and the returning
plasma light are transmitted through a transparent atmosphere.
This approach, generally named stand-off LIBS, allows analysis
of physically inaccessible targets which may be located in
hazardous environments where presence of an operator is not
possible but optical access is possible through a transparent
atmosphere. It also allows rapid analysis of separated targets
from a single point, screening of large surfaces by laser
scanning, and avoids damage or contamination of instrumen-
tation by harsh environments.
useful plasma at distance and collecting sufficient light,
imposing constraints on the specifications of the laser, the
optical system used for laser focusing and plasma light
collection as well as on the spectrograph and detector. Two
different methods of stand-off LIBS measurements have been
demonstrated generating analytically useful plasmas. The first
method has used nanosecond laser pulses with the required
energy dependent on the target distance and the characteristics of
the optical system to produce power densities sufficiently high to
form a plasma (typically ≥ 1 GW/cm2). It has been mainly
demonstrated for the analysis of solid targets at a distance range
of tens of meters. Liquid samples have also been analyzed at
distances of a few meters. Due to the high-power densities
required to induce gas breakdown, stand-off LIBS analysis of
gases has not been yet reported. The second stand-off LIBS
method has employed femtosecond laser pulses either in
conventional LIBS or by using the self-guided filaments induced
in the transparent medium (air) that propagate over long
distances and produce excitation of the sample. This method
can extend the analysis at very long distances with kilometer
range predicted. The majority of open-path stand-off LIBS
measurements have been realized using nanosecond pulses, the
femtosecond method requiring the use of sophisticated laser
systems still under development. Different optical arrangements
have been tested depending on the envisaged application. One of
the first studies on stand-off LIBS analysis of solids has been
published in 1987 [3] with the aim of demonstrating the rapid
sorting of metals at a distance less than 3 m. The following
studies have concerned the stand-off analysis of geological
samples to promote LIBS as an analytical instrument for future
planetary missions. A great number of publications have
reported real-time stand-off LIBS analysis of stainless steel
samples for process control and monitoring in metallurgical
industry. Stand-off LIBS has also been used for situations where
elemental composition of radioactive environments was needed
in the nuclear industry. Other reported works have been aimed to
detect contamination with civilian and military applications. The
first results on stand-off LIBS with femtosecond laser pulses
have been published in 2004 on metal samples [4] at 25 m using
conventional LIBS and at 90 m using filamentation in air [5].
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
The aim of this review is to present a brief overview of the
results of studies on stand-off LIBS analysis and its recent
applications. First, we will discuss the LIBS fundamentals
which impose constraints on the stand-off instrumentation
specifications. Secondly, the stand-off LIBS analysis using
nanosecond laser pulses will be described with the different
experimental configurations used for laser focusing and plasma
light collection at long distances, and the different applications.
Then, we will describe the stand-off LIBS analysis using
femtosecond laser pulses with either the conventional LIBS
scheme or the self-guided filaments induced in the atmosphere.
Finally, we will synthesize the analytical performance obtained
in the stand-off LIBS experiments.
2. LIBS fundamentals for the design of a stand-off
instrument
In this part, we will describe the characteristics of laser
ablation and laser plasma induced at a distance and, their
influence on the specifications of a stand-off LIBS instrument.
The aim of this part is to understand the instrumental choices
realized by the different LIBS research groups during years,
depending on the applications.
The LIBS technique is based on the focusing of high-power
laser pulses onto a sample surface leading to the creation of a
plasma composed of excited species which emit light.
Collection of the plasma light, followed by spectral dispersion
and detection, permits identification of the elements present in
the sample using their characteristic spectral lines (qualitative
analysis) and measurement of their intensities provides
quantitative analysis. LIBS quantitative results are usually
obtained by deducing the concentration of an element in an
unknown sample from a calibration curve which represents the
intensity for the element line as a function of the elemental
concentration in reference samples analyzed in the same
experimental conditions. However, the spectral emission
intensity in the plasma is determined not only by the
concentration of the element in the sample, but also by the
properties of the plasma itself, which depend on factors such as
the sample, the surrounding gas, and the characteristics of the
laser, e.g. wavelength, energy, power density. As the analysis
distance will grow, the power density on the target will
decrease. Then, quantitative analysis at stand-off distance is a
difficult task, mostly because the standard approach of
calibration through reference materials is not directly applica-
ble. In a laboratory, the analysis distance is fixed and the
analyzed samples and the standards can be placed in exactly the
same experimental conditions contrary to field analyses of
complex and a priori unknown samples. Moreover, as for any
method of direct solid sample analysis, the accuracy of
quantitative results is often limited by the matrix effects as the
analytical response is influenced by the physical properties of
the sample, as well as its overall chemical composition.
Therefore, the physical processes originating the spectra must
be characterized and modeled to develop calibration-less
procedures leading to quantitative analysis at different dis-
tances. It is of prime importance for stand-off LIBS analysis to
741
understand and control the ablation process and the plasma
characteristics in order to achieve accurate and sensitive
quantitative analysis.
The hypothesis of stoichiometric ablation, i.e. the material
excited in the plasma has the same composition as the sample,
forms the basis of the LIBS method. Laser ablation has been
demonstrated to be stoichiometric when the power density on the
target exceeds 1 GW/cm2 [6] but in general, it is related to the
optical properties of the sample, the wavelength of the laser – a
shorter laser wavelength tends to provide better stoichiometry –
and significantly, the laser irradiance (fluence and pulse
duration) [7]. Shorter pulses are beneficial for better stoichio-
metric ablation process. A possible explanation is that for shorter
laser pulse duration, less laser energy is lost through thermal
dissipation, reducing elemental fractionation. The crater depth
and its aspect ratio also influence stoichiometry but no exact
mechanism for this effect is established. One hypothesis is that
the plasma generated inside a deep crater may contribute to the
sampling process, leading to elemental fractionation. Another
possibility is that the irradiance decreases as the crater deepens
due to a larger surface area of the crater, and reduces to values
below the threshold for stoichiometric ablation. The value of
1 GW/cm2 is commonly reached in LIBS measurements with
laser pulse durations typically in the range of 5–10 ns depending
on the type of laser. These pulses contain energies ranging from a
few mJ up to 1000 mJ with the fundamental wavelength of
1064 nm preferred for stand-off applications, resulting in pulse
powers of 0.3 to 100 MW. For a given laser pulse power, the
power density generated on a remote sample will mainly depend
on the minimum achievable spot radius w which, as shown by
Eq.(1) for a Gaussian laser beam, is a function of the analysis
distance r, the beam quality parameter M2, the laser wavelength
λ and the laser beam diameter at the focusing optics D:
2kr 2
w¼ M : ð1Þ
pD
For a high quality laser beam (like a Gaussian beam charac-
terized by M2 = 1), the spot size is governed by spherical
aberrations in the optical system and by the diffraction limit.
Obeying the laws of classical optics, the diameter of focus
linearly increases with focusing distance as a consequence of the
diffraction. The use of nanosecond pulsed laser for excitation is
limited in the range of operation by difficulty to tightly focus the
laser beam at long distances. Increase of operation distance
would require exorbitant large laser energy and large focusing
optics which would become prohibitive for practical uses. At
long distances with nanosecond lasers, the mentioned irradiance
threshold of 1 GW/cm2 for a stoichiometric ablation process
may not be reached. Recently, picosecond and femtosecond
lasers, generating pulses of durations on the order of 10− 12 and
10− 14 s and powers from hundreds of MW to tens of TW, have
been investigated for remote LIBS applications with the aim of
increasing the analysis distance. Another important parameter
for laser focusing is the depth of focus DOF of the beam which is
a measure of how accurately the focus must be adjusted to
produce the greatest power density on the remote sample. It is
defined as twice as long as the Rayleigh length, which is the
742 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
distance between the two positions from the laser waist at which
the area of the beam has doubled:
8k  r 2 2
DOF ¼ M ð2Þ
p D
Eq. (2) shows that the depth of focus varies as the square of the
analysis distance and as the reciprocal of the square of the input
beam diameter. As a consequence, the greater the analysis
distance, the longer the depth of focus and hence precise
focusing becomes less crucial.
Although a laser pulse may have focused irradiance on the
order of GW/cm2, if the pulse energy is too low, sufficient
material may not be vaporized to provide an analytically useful
emission signal. Therefore, the use of high quality anti-
reflection optics is important to maximize the laser energy on
the target which can also be reduced through absorption and
scattering by the atmosphere and aerosol particles. The beam
guiding components play a crucial role as it must accomplish
the task of focusing laser energy on the sample surface to a
sufficient small spot to provide the necessary irradiance to
produce a plasma without inducing undesired breakdown of the
air along the laser path on the vicinity of the target, which is
favored by the presence of particles emerging from the
analytical plasma. Expanding the laser beam prior to focusing
is essential to reduce the focused spot size at far distance and
avoid the air breakdown, which greatly depends on the incident
laser wavelength. In addition, certain laser wavelengths couple
more strongly into specific materials compared with other
wavelengths, depending on materials absorption properties. The
choice of the laser wavelength is also important for ocular and
skin safety of the public and operator, in particular with the use
of a stand-off LIBS instrument: the hazards increase as the laser
path length grows.
The laser energy, the laser irradiance and therefore the
analysis distance influence the plasma size which also depends
on the observation delay [8–14]. Indeed, soon after plasma
initiation, the spectrum is dominated by a strong continuous
emission background due to Bremsstrahlung (photons are
emitted by free electrons accelerated or decelerated in collisions
with ions or atoms) and to recombination (free electrons are
captured into ionic or atomic energy levels and give up their
excess kinetic energy in the form of photons). Additionally,
emission from ionic species is superposed to this background.
After the laser pulse has terminated, the plasma decays over
several microseconds, depending on the laser energy deposited
and on the environmental conditions (gas and pressure). As the
plasma decays, one observes a decrease of the continuum and of
the intensity of ionic lines due to the recombination of free
electrons with ions, and the spectrum becomes composed of
neutral atoms emissions. Then, emission of simple molecules
formed from the recombination of atoms can also be observed in
the spectrum. If the plasma light is integrated over the entire
lifetime of the plasma, the continuum light interferes with the
detection of the element lines and this is seriously observed at
atmospheric pressure. For this reason, LIBS measurements are
usually carried out using time-resolved detection. Thus a time
delay (typically between a few tens of ns and a few μs) is usually
applied between the initiation of the laser and the opening of the
gate during which the emission signal is recorded and for which
width has to be optimized (typically between a few hundred of ns
and several μs). The optimum time gating parameters depend on
many factors including laser wavelength, power density at the
target surface, sample composition and physical state, ambient
gas pressure, considered emission line. They have to be chosen
for significantly decreasing the continuum, improving the signal
to background ratio, and thus helping to extract the spectral
features [15–21]. An additional and important factor has to be
taken into account in stand-off LIBS analysis with temporal
resolution: this is the delay introduced by the measurement
distance. In usual LIBS experiments, the spectrometer is
triggered on the Q-switch out of the laser and the reference for
signal acquisition is the firing of the laser pulse. For stand-off
analysis, an additional 6.6 ns delay per every meter (speed of
light) from the laser to the sample where plasma light emission
occurs has to be taken into account. At 80 m for example, the
extra delay of approximately 530 ns can greatly change the
characteristics of the acquired spectrum. As a consequence,
attention has to be paid when LIBS spectra recorded with
temporal resolution at different distances have to be compared
because of the acquisition reference time.
The plasma size also strongly depends on the surrounding
gas. The pressure and nature of the ambient gas influence the
plasma expansion, the laser–plasma interaction and thus the
absolute line intensities and the line widths. The two main
competing processes occurring with pressure variations are
changes in ablated mass and changes in plasma excitation
parameters (electron density and temperature). As the pressure
is increased, the mass of ablated material decreased significantly
due to higher plasma shielding [22]. On the other hand, a
pressure increase induces a confinement of the plasma near the
sample surface [22–28], increasing the number of collisions
responsible for excitation of species in the decaying plasma.
Another factor can explain the variations in intensities observed
with pressure changes: as the pressure is reduced, the atomic
species are no longer confined at the target surface and may no
longer be in the field of view of the light collection system
giving an apparent decrease in excitation [29]. Thus, it is
necessary to estimate the size of the plasma produced in the
specified experimental conditions to define the optimum optical
system used to collect and image the plasma light onto the
detection system (spectrograph and detector). The amount of
collected plasma light is limited by the smallest geometric
extent (or etendue) of the LIBS setup. In general, for analysis at
short distance, it is limited by the spectrograph whereas at stand-
off distance, it can be limited by the diameter of the optics of the
collecting optical system. The LIBS signal must be proportional
to the solid angle of collection, which is a function of the inverse
square analysis distance. It means that, by supposing that the
plasma conditions are not changing with the working distance, a
LIBS signal of 16,000 counts at 1 m will be of 4000 counts at
2 m, 640 counts at 5 m and only 160 counts at 10 m.
The plasma light can be collected collinear with or off-axis to
the path of the laser pulses directed on the target. This last setup
presents a higher complexity of operation in stand-off LIBS
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
since it requires successive pointing of both laser focusing and
plasma collection optics as the target position changes with the
analysis distance. The coaxial scheme enables a much simpler
operation due to the fact that the both light paths, laser and
plasma, share the same optical axis. In the collinear arrange-
ment, the plasma light must be diverted from the path of the
laser pulses and several configurations can be envisaged. One
configuration can use a beam splitter which must have a coating
that passes the laser wavelength but reflects the plasma light
over a wide spectral range (typically from the ultraviolet UV to
the visible VIS range). Due to the coating, some spectral regions
are not efficiently reflected from the beam splitter making this
configuration not ideal for wide spectral region detection. The
use of an aluminized mirror with a central aperture to pass the
laser beam avoids this problem but induces a loss of returning
plasma light due to the large central aperture in the mirror
required by the greatly expanded laser beam in stand-off
analysis. In the majority of LIBS experiments, the converse
arrangement to the previous one is used to separate the plasma
light from the laser beam: the laser pulses are directed onto the
target by a 100% reflecting mirror which transmits the plasma
light in the same axis as the laser beam. The plasma detection is
still limited at some spectral regions because the wavelengths
around the harmonics of the laser wavelength are not efficiently
transmitted by the mirror coating. The plasma light focusing can
be realized either onto an optical fiber or directly on the entrance
slit of the spectrograph. This can be performed either by
reflecting or refracting components. These last components
must be made from UV-transmitting materials, corrected for
chromatic aberration in the UV–VIS range, and these require-
ments increase the cost. Chromatic aberration results from the
variation of the material refractive index with the incident
wavelength. The consequence is that different wavelengths are
focused at different points along the optical axis and the fiber
optic or the spectrograph has to be moved relative to the optical
refractive component to optimize the emission intensity
collected for different spectral ranges. It means that when
using an Echelle spectrograph with a large spectral window
(typically 200 to 900 nm), it is not possible to optimize the
signal on the whole spectrum region. The setup will be free of
chromatic aberration by choosing achromatic lenses in which
this effect has been corrected or a mirror in the place of the lens.
In addition to the width of spectrum that can be observed
(typically a wider band of observable spectrum is needed when
several elements are monitored simultaneously, for example
C at 247.8 nm with Cl at 837.5 nm or S at 180.2 or 921.2 nm),
another important characteristic of a LIBS apparatus is the
spectral resolution, e.g. the minimum wavelength separation at
which two adjacent spectral features can be observed as two
separate lines. The spectral resolution must be defined from the
number and the type of elements to be monitored to avoid
spectral interferences between the element lines of interest. The
optical collection system, the spectral selection device and the
detector system, all have a characteristic wavelength dependent
efficiency which implies that each experimental apparatus
exhibits a unique spectral response. The LIBS measurements
are a convolution of the plasma physical data and of this
743
wavelength system response which has to be experimentally
determined in situations where accurate relative line intensities
are required by using a large number of lines in a wide spectral
range.
3. Stand-off LIBS analysis with nanosecond pulses
3.1. Instrumentation
As previously seen, the distances achievable in stand-off
LIBS analysis depend on the specifications of the laser, on the
optical system used to focus the pulses at a distance and on the
efficiency of the plasma light collection system.
3.1.1. Laser systems
The majority of works reported on stand-off LIBS analysis
have employed nanosecond laser pulses. LIBS analysis of
liquids has required specifications on laser pulse repetition rate
and LIBS applications to space exploration have imposed
constraints on size, weight and electrical power of laser.
Flashlamp-pumped pulsed and Q-switched Neodymium-doped
Yttrium Aluminum Garnet (Nd:YAG) lasers having pulse
widths in the 6–15 ns range have been typically used for
stand-off LIBS measurements with the fundamental 1064 nm
wavelength providing the highest energy. However, a few
exceptions have been encountered depending on the envisaged
applications. One of them concerns a new type of remote-
sensing instrument named ChemCam [30,31] which has been
selected for the mobile Mars Science Laboratory (MSL) rover
scheduled for launch in 2009 [32], to investigate with the LIBS
technique the Martian surface at a distance between 2 and 9 m
from the rover. Because of size, weight, power consumption
constraints in space missions, the ChemCam laser design is
based on a commercial compact diode-pumped Nd:YAG laser
but a new crystal inducing emission at 1067 nm replaces the
YAG to boost the gain and enlarge the thermal acceptance (due
to expected operations over 40 °C temperature range with no
thermal control). Another exception relates the remote detection
of contamination with applications toward cultural heritage, for
which a mobile lidar (light detection and ranging) system
housed in a truck has been employed [33]. The tripled radiation
(355 nm) was selected instead of doubled (532 nm) or
fundamental (1064 nm) radiation for eye-safety considerations
and because this laser wavelength allowed application of laser-
induced fluorescence spectroscopy to obtain complement
information. Higher energies are required to form the plasma
at longer distances, typically between 20 and 1650 mJ at
1064 nm to reach distances of tens of meters. With the laser at
355 nm, a pulse energy of 150 mJ generated a plasma on metal
samples positioned at a distance of about 60 m.
3.1.2. Optical systems for laser focusing
For analyses at fixed distances, the laser pulses may be
focused using a simple lens or a concave spherical mirror. The
disadvantage of such optical system is that it is necessary to
change its focal length or move the LIBS system when the
analysis distance is changed. Table 1 gives an overview of
744 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768

Table 1
Laser focusing systems with refracting optics for stand-off LIBS analysis with nanosecond pulses
Ref. Optical system for Laser wavelength– Focusing Samples Environment Plasma collection
laser focusing energy distance
One single lens
[3] 1064 nm–45 to 475 mJ 55 cm Brass, Monel, steel Fiber optic
1064 nm–227 mJ 2.41 m Steel Off-axis configuration: lens
F = +5 cm, fiber optic
[34] F=1 m 1064 nm–250 mJ 4 ma Mineral melt 1600 °C Off-axis configuration: lens
F = 1 m, lens F = 100 mm,
fiber optic
[35] F=5 m 1064 nm–250 mJ 6m Aluminum 20 °C Off-axis configuration:
reflection by 3 flat mirrors,
1 pierced mirror.
1064 nm–390 mJ Stainless steel 600 °C Collection at 25, 80, 100 m
by a Newton telescope

Galilean telescope
[35] 1064 nm–1500 mJ 12 m Stainless steel 20 °C and 1200 °C Pierced Al mirror, Newton
telescope
[38] Variable lens 1064 nm–334 mJ Up to 1.5 m Liquid steel Ar high temperature Pierced Al mirror, lens, fiber
system optic bundle
[39] F = − 25 mm 1064 nm–230 mJ 35 to 45 m Stainless steel Off-axis configuration:
F = +300 mm refractor telescope
12×
[40] F = − 22.25 mm 1064 nm–820 mJ 10 to 100 m Aluminum Same as [35]
F = +198.84 mm
8.9
[41] F = − 22 mm 1064 nm–900 mJ 10 m Stainless steel 20 °C to 1200 °C Same as [35]
F = +200 mm
9
[42] F = − 62.1 mm 1064 nm–1650 mJ 10 m Moving stainless steel Dichroic mirror, Newton
F = +198.84 mm telescope
3.2
[43] Same as [40] 1064 nm–1500 mJ 12 m Environmental samples Pierced Al mirror, Newton
telescope, fiber optic, couple
of lenses
[44] Same as [40] 1064 nm–1500 mJ 12 m Steel slag samples Same as [43]
[45] Same as [40] 1064 nm–1500 mJ 12 m Stainless steel samples 25 °C to 1000 °C Same as [43]
[46] 4 1064 nm–320 mJ 24 m Volcanic tuff A few Torr Dichroic mirror, lens of
10 1064 nm – 10 m Rock samples larger diameter, fiber optic
1064 nm–500 mJ 10.5 m Simulated rocks from
Apollo 11 moon mission
[22] Galilean telescope to 1064 nm–80 mJ 19 m Soils, stream sediments, 7 Torr CO2 Same as [46]
reduce the beam diameter synthetic silicates
(from about 7 to 2.3 mm) 1064 nm–35 mJ 19 m Soil
to match the input of a
20 commercial beam
expander
[47] 10 1064 nm–100 mJ Water ice and water ice/ Atmospheric pressure Same as [46]
soil mixtures air, 7 Torr air, 7 Collection at 4 and 6.5 m b
Torr CO2
165 K and 246 K
[48] 7 1064 nm–85 mJ 2 to 6 m Rock powder standards Quartz plate, fiber optic
and rock samples
collected from the field
[49] Same as [46] 1064 nm–40 mJ Basalt, soil, stream 7 Torr CO2 Same as [46]
sediment standards and Collection at 5.3 m b
basalt rock from the field
[50] F = − 100 mm 1064 nm–31 mJ 3, 5, 8,12 m Aluminum, basalt 9 mbar of gas mixture Quartz plate, lens, fiber optic
F = +400 mm CO2, N2, Ar
4
[51] Same as [46] 1064 nm–24 mJ Martian basaltic shergottite 7 Torr CO2 Same as [46]
meteorites Dar al Gani 476 Collection at 5.4 m b
and Zagami, basalt and
andesite rock powder
standards
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768 745

Table 1 (continued )
Ref. Optical system for Laser wavelength– Focusing Samples Environment Plasma collection
laser focusing energy distance
Galilean telescope
[52] 5x 1064 nm–55 mJ 8.3 m Mineral samples (sulfates, Off-axis configuration:
carbonates, silicates) Maksutov–Cassegrain
telescope, couple of
lenses or commercial
reflecting telescope, couple
of lenses, fiber optic
[53] 10x 1064 nm–~200 mJ ~10 m Mineral samples (calcite, Off-axis configuration:
dolomite, gypsum, Maksutov–Cassegrain
magnesite, pink coral) telescope, lens, 10x
microscope objective,
fiber optic, couple of lenses

Kepler telescope
[54] 5 1064 nm–30 mJ 2 to 5 m Aqueous solutions Off-axis configuration: lens,
fiber optic (~ 10°)
On-axis configuration:
frustrated total internal
reflection beam
separator, fiber optic

System at three lenses

[50] F = − 100 mm 1064 nm–31 mJ 3m Aluminum samples 9 mbar of gas Quartz plate, lens, fiber optic
F = +300 mm Pyrite, covellite, sulfur, mixture CO2, N2, Ar
F = +3000 mm galena, NaCl
[55,56] F = − 25 mm 355 nm–170 mJ 60 m Metal samples Pierced Al mirror, Newton
F = +500 mm Stone samples telescope, fiber optic
F = +1000 mm Statues
[57] Same as [55,56] 355 nm–25 mJ 60 m Electrode material copper Same as [55,56]
Added lens F = +50 cm Insulator silicon rubber
[58] Same as [50] 1064 nm–25 mJ 3m Volcanic rocks, gabbro, 9 mbar CO2 Same as [50]
limestone
[59–65] LIBSCAN50 1064 nm–40 mJ 0.1 to 5 m Nuclear applications Dichroic mirror, UV mirror,
LIBSCAN400 1064 nm–300 mJ 0.1 to 15 m lens, fiber optic
a
Distance between the laser and the target.
b
Distance from the sample to the lens or telescope used for plasma light collection.

studies which use a simple lens for laser focusing, evidencing
that the maximum analysis distance achieved with such focusing
system is about 5 m. Cremers [3] compared the light intensity
collected from a spark generated by focusing a Nd:YAG laser on
metal surfaces via a simple lens for lens to sample distances of
55 cm and 2.41 m. For the remote analysis of a mineral melt,
Panne et al. [34] tested a customized mobile LIBS system during
a field campaign of mineral wood production. A Nd:YAG laser
was fixed at the end of an optical rail 4 m in length whereas the
laser focusing lens (f = 1 m) was located on the opposite side of
the rail mounted on a mobile platform. During operation, the
laser module was positioned near the furnace, its distance to the
melt was optimized via the signal to noise ratio of the Si line at
288.1 nm and a lens to sample distance of 1 m was sufficient to
minimize the risk of damaging the optical system by debris from
the melt. The laser module was removed when access by
maintenance personnel was necessary to remove debris from the
melt or to straighten the melt flow. In one of the two optical
configurations used for remote analysis of high-temperature
aluminum and stainless steel samples, Vadillo et al. [35] focused
the laser pulses with a 5 m focal length lens and performed the
plasma light collection at three different distances (25, 80 and
100 m) (see Fig. 1). For the chemical analysis of metal melts
present in a metallurgical vessel, Ramaseder et al. invented a
LIBS device equipped with movable arms [36–38]. In a first
case, the laser focusing system was formed by a convex lens or a
concave spherical mirror with a focal length adapted to the
distance to the metal bath. In a second case, the laser focusing
system was formed by one concave lens and one convex lens,
and it was tested for analysis of solid and molten metals at
variable distances up to 1.5 m [38] (see Fig. 2).
As shown previously in the work presented in [38], when the
analysis distance needs to be adjusted, a pair of lenses or a
commercial beam expander may be used to vary the position of
the focal point. The more usual optical system used in stand-off
LIBS analysis is a Galilean telescope composed of one concave
lens and one convex lens. For each distance, the spacing between
the lenses is adjusted to produce the plasma yielding the most
intense spectra. Table 1 summarizes the different works that used
a Galilean telescope for laser focusing with the range of distance
and the samples investigated [22,35,38–53]. In the majority of
works reported in the literature, the analysis distance is defined
as the distance from the focusing lens to the sample surface, but
in some reports, the indicated distance corresponds to the
746 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
Fig. 1. Experimental setup used for remote monitoring of high-temperature
samples by LIBS. L laser, FL focusing lenses, M1, M2, M3 flat mirrors, PM
pierced mirror, T telescope, SP spectrograph, MD multi-channel detector, DG
digital delay/pulse generator, PC personal computer. With kind permission of
Springer Science and Business Media.
distance between the lens used for plasma light collection and
the sample. Table 1 shows that using a Galilean telescope, it is
possible to focus laser beam up to 100 m with energy of 820 mJ.
For analysis of liquid samples [54], the Galilean telescope was
replaced by a Keplerian telescope expanding the laser beam
Fig. 2. Setup showing the optics for laser beam focusing and for coupling the plasma light emission into the fiber optic bundle. Reproduced by permission of Elsevier.
diameter from about 8 mm to about 4 cm. The focal length of this
line-of-sight telescopic assembly was adjustable in the range 2 to
5 m. The Keplerian telescope which uses a converging lens
instead of a diverging one allows for a much wider field of view
and considerably higher magnifications than the Galilean
telescope, which, on the other hand, leads to a more compact
design. The use of a Keplerian telescope is limited by the
breakdown of the air after the first converging lens.
When Galilean or Keplerian telescope is employed to focus the
laser pulses, the use of high quality anti-reflection coated optics is
important to maximize the power density transmitted to the target.
For example, photograph of the spot produced after 100 laser
shots on a stainless steel sample in [39] showed a central crater
with a surrounding concentric crown which was attributed to both
thermal effects and aberrations induced by the two lenses used for
laser focusing. In the same way, by using two lenses for the
variation of the focusing distance [50], a decrease in the total
plasma emission (represented by the number of photons emitted
by the plasma per steradian) was observed as the lens to target
distance increased. This effect was explained by the variation of
the laser fluence (energy per unit of area) on the target and by the
change of the laser intensity distribution evidenced by the
appearance of a multiple-ring structure around the craters formed
onto the sample surface due to the use of a multi-mode laser and to
spherical aberration introduced by the lenses doublet. The authors
concluded that for LIBS analysis at stand-off distances, it was
necessary to use a good spatial laser intensity distribution and
high quality optics (aberration limited).
To reduce the spherical aberration and thus obtain a tighter
focus spot size, a divergent lens and two positive lenses were
used instead of one to focus the laser [33,55–57]. For detection
of contamination, they employed a mobile lidar system in which
the laser beam was first expanded and transmitted through a
specially designed low-aberration telescope consisting of one
plano-concave lens (f = − 25 mm) and two plano-convex lenses
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768 747

Table 2
Laser focusing systems with reflecting optics for stand-off LIBS analysis with nanosecond pulses
References Optical system for Laser wavelength–energy Focusing distance Samples Environment Plasma collection
laser focusing
[30] Galilean telescope 1067 nm–5 to 30 mJ 2 to 9 m Rocks and soils Martian atmosphere Schmidt–Cassegrain telescope,
Schmidt–Cassegrain dichroic mirror, fiber optic
telescope
[37] Concave spherical 1064 nm–350 mJ High temperature Pierced mirror, lens, fiber optic
mirror of F = 4 m or bundle
F = 2.5 m 4m Liquid steel ~1 mbar Ar or N2
2.5 m Ni based alloy 0.2 mbar Ar
[66] F = − 500 mm 1064 nm–220 mJ 7.5 m Stainless steel 20 °C and 1420 °C Concave Al mirror, dichroic
Dichroic mirror mirror
Flat Al mirror
Concave Al mirror
[67] F = 189 mm 1064 nm–350 mJ 25 to 95 m Metal samples Concave Al mirror, dichroic
F = − 62.1 mm mirror, fiber optic
Dichroic mirror
Herschelian telescope
[68] Same as [67] 1064 nm–350 mJ 30 and 45 m Energetic materials Same as [67]
[69] Al primary mirror 1064 nm–up to 1200 mJ 2 to 12 m

(10 cm diameter, f = +500 and +1000 mm) spaced by about 20
and 25 cm. The lens diameter was chosen to minimize the focus
with regards to both aberration and diffraction. While a focal
spot diameter of about 0.7 mm was calculated at a distance of
60 m, in practice burn-marks showed a focus diameter of about
5 mm. This type of setup was also used by Sallé et al. [50,58] to
study the capability of LIBS for stand-off analysis in a
simulated Martian atmosphere. They used a 3× beam expander
composed of two lenses f = − 100 mm and f = +300 mm and
focused the laser pulses onto the sample with a 3 m focal length
lens. Principally for nuclear industry measurement applications
[59–65], the optical schemes of the LIBSCAN custom
instrument based on LIBS presented in [59,60] showed a laser
focusing system composed of a Galilean telescope and a
focusing lens. This system operated either as a telescope device
over distances of up to 15 m or as a fiber optic probe device over
distances of up to 50 m. Two versions of the instrument were
available depending on the laser and on the telescope operating
range. For the telescope mode, the LIBSCAN50 delivered pulse
energy of 40 mJ for an analysis distance from 0.1 to 5 m, and for
the LIBSCAN400, laser energy was 300 mJ for an analysis
distance comprised between 0.1 and 15 m. Table 1 which
presents all these configurations shows that using three lenses
for laser focusing allows reaching an analysis distance of 15 m
and 60 m with a laser wavelength of respectively 1064 nm and
355 nm.
More sophisticated optical systems combining mirrors and
lenses have also been utilized for laser focusing. The focusing
distance can be adjusted to interrogate from a fixed position,
samples placed at different ranges. Table 2 gives an overview of
the different laser focusing systems found in literature with
detailed description in the next section. It shows that analysis

Fig. 3. Setup of the transportable LIBS instrument used for analytical control of liquid steel in an induction furnace. 1 Laser, 2 focusing and collection optics, 3 laser
power, delay generator and computer, 4 folding mirror, 5 focusing mirror, 6 induction furnace, 7 crucible. Reproduced by permission of The Royal Society of
Chemistry.
748 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
distance of about hundred meters can be achieved by using
reflecting optics for laser focusing.
As previously discussed, Ramaseder et al. constructed a
LIBS device equipped of movable arms with the focusing
system composed of either a convex lens or a concave spherical
mirror [36]. This last device was tested for analysis of liquid
steel at 4 m from the focusing mirror and of a Ni based alloy at a
distance of about 2.5 m [37]. Palanco et al. [66] designed a
transportable open-path LIBS instrument for quality control of
liquid steel in an induction melting furnace. The vertical access
to the induction furnace and the short analysis distance
attainable at the laboratory were the two principal factors
which determined the optical design of the instrument shown on
Fig. 3. The laser beam was expanded by a plano-concave lens of
focal length f = − 500 mm and then was folded by a dichroic
mirror towards a flat aluminum mirror and then towards an
aluminum concave mirror (radius of curvature = 2048 mm),
which focused the beam to the melt surface of the sample. Due
to the off-axis configuration used with this mirror, the optical
aberrations yielded an ellipsoidal spot of about 2 × 4 mm at the
steel surface. With such a system, ablation of stainless steel
samples at room temperature and at 1420 °C was realized with
laser energy of 220 mJ for an analysis distance of 7.5 m.
In [67], the same group described the design and the
construction of a field-deployable LIBS instrument based on a
Herschelian telescope (Fig. 4) and capable of approaching
distances of measurement in the hundred of meters. The
diverging elements were a pair of lenses (diameter = 25.4 mm
and focal lengths 189 and − 62.1 mm), the primary mirror of the
telescope was a parabolic reflection-enhanced aluminum mirror
(203.2 mm diameter, f/10) to prevent spherical aberration and
only an off-axis section was used to transmit the laser beam and
reduce astigmatism and comma. A motorized flat aluminum
mirror was used to fold the telescope axis, making it more
compact, and to change the distance between the diverging
Fig. 4. Schematic of the field-deployable LIBS instrument, 1 laser, 2 folding mirror, 3 lenses, 4 dichroic mirror, 5 focusing mirror, 6 primary mirror, 7 fiber optic cable,
8 spectrograph, 9 detector, 10 personal computer, 11 laser power supply. Reproduced by permission of Elsevier.
lenses and the primary mirror, allowing the system focus
adjustment. The performance of this system was tested on
metallic samples up to 95 m for laser energy of 350 mJ. It was
also used for ablation of energetic materials placed at distances
of 30 and 45 m [68].
A commercial transportable LIBS system named TeleLis
[69] was proposed for remote chemical elemental analysis. The
system employed a 300 mm aluminum coated primary mirror
allowing to reach analysis distances in the 2–12 m range with a
maximum pulse energy of 1200 mJ and the double pulse option.
The optics could also be designed for other operation ranges on
request.
For space applications where instrument mass is important, a
mirror system is desirable because mirrors can generally be
fabricated having less mass than an equivalent lens. The
ChemCam instrument proposed for the MSL rover [30] will use
a Galilean telescope and then a compact Schmidt–Cassegrain
telescope composed of a perforated spherical primary mirror
(100 mm diameter), a convex secondary mirror (32 mm
diameter) and a Schmidt plate to correct for spherical aberration
caused by the primary mirror. The secondary mirror will be
mounted on a translation stage with a stepper micro-motor
covering a 10 mm range in order to achieve focusing from 2 to
9 m with an output laser energy adjustable from 5 to 30 mJ.
3.1.3. Optical systems for plasma light collection
In the first study reported on stand-off LIBS analysis of
solids [3], the authors demonstrated that collection of the
plasma light could be realized in at least two ways. For a lens to
sample distance of 0.5 m or less, a fiber optic could be directly
used to collect and transmit the plasma light to the detection
system. It was shown that the light intensity collected by the
fiber was relatively insensitive to moderate changes in the lens
to sample distances (ranged from 0.47 to 0.74 m) and in the
horizontal position of the laser focusing lens due to the large
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
acceptance angle of the fiber. For a lens to sample of 2 m or
more, the plasma light had to be focused on the end of an optical
fiber by using a lens in order to collect a much larger fraction of
the light. A disadvantage of this arrangement was that the
collected light intensity was more sensitive to changes in the
plasma position which could move the plasma image off the
spectrograph slit. For a lens to sample distance between 0.5 and
2 m, the need for a lens to focus the light on a fiber will be
determined by the strength of the analytical lines and the type of
analysis required (qualitative or quantitative).
Following this study, the systems presented in Tables 1 and 2
have been developed in which the plasma light was collected
collinear with or off-axis to the path of the laser beam directed to
the target. First, we present the studies employing an off-axis
configuration.
For remote analysis of stainless steel samples [39], the light
emitted by the plasma was collected in an off-axis configuration
to the laser with a conventional refractor telescope (60 mm
diameter, f = 400 mm, f/8.3) whose the flange was adapted to
the entrance slit of a spectrograph. The Cr emission signal at
540.97 nm was observed to decrease for laser incidence angles
beyond 40°. This effect was explained by a decrease of the laser
fluence on the target for such angles and/or by changes in the
amount of collected plasma light due to the off-axis configu-
ration. The Cr emission from steel samples was also studied in
[35] where the plasma light was reflected by three flat mirrors
and a pierced mirror (300 mm diameter with a clear aperture of
120 mm diameter) before being collected by a Newtonian
telescope (f = 800 mm, 200 mm diameter, f′ = ∞, 32 mm
diameter) adapted to the entrance slit of a spectrograph (see
Fig. 1). The first collecting mirror was placed at an angle from
the laser axis. Modification of the relative distance between the
three mirrors allowed performing the collection at three
different distances (25, 80 and 100 m) which were not the
same as the laser focusing distance (6 m). This configuration
implied plasma light loss due to the use of both the first
collecting mirror whose diameter was not adapted to the plasma
emission angle and the pierced mirror.
LIBS combined with pulsed-laser Raman spectroscopy was
evaluated in laboratory for mineral analysis at distances of 8.3
and 10 m [52,53] with the aim of using such a combined
instrument for planetary applications. In [52], the plasma light
was collected by two telescopes. The first one was a commercial
Maksutov–Cassegrain telescope (127 mm clear aperture, 1.9 m
focal length) in which the complexly shaped corrector plate of
the Schmidt–Cassegrain telescope is replaced by a curved lens
correcting for the spherical aberration and easier to manufacture.
This telescope gives better resolution than the Schmidt–
Cassegrain telescope but tends to have a narrower field of
view due to its longer focal length and is generally heavier
making it less adapted for spacecrafts. Light from the
Maksutov–Cassegrain telescope was focused at the entrance
slit of a spectrometer by a two lenses system. The second
telescope was a commercial reflecting telescope (11 cm
diameter) from which light was focused, using two lenses, into
a 500 μm optical fiber connected to a spectrograph. In [53], the
Maksutov–Cassegrain telescope also collected plasma light
749
which was collimated by a lens and then focused by a 10x
microscope objective onto an optical fiber. The light leaving the
fiber was collimated by a lens and then focused by an objective
lens at the entrance slit of a spectrometer.
For remote analysis of a mineral melt with a customized
mobile LIBS system [34], the plasma emission was collimated
with a lens (50 mm diameter, f = 1 m) at an angle from the laser
axis and then focused via a second lens (50 mm diameter,
f = 100 mm) on a fiber optic (550 μm diameter, 15 m length)
connected to a spectrometer. The signal to noise ratio of a Si line
was observed strongly dependent on the distance between the
laser and the melt. This was caused by the angled observation
geometry where changes of the laser position relative to the melt
resulted in the collection of a slightly different plasma region and
in variations of the elemental emission. The authors indicated
that a collinear geometry for plasma formation and collection
will avoid these problems. For remote analysis of liquid samples
[54], the plasma light was collected onto the fiber optic of a
spectrometer using a lens with an angle of about 10° relative to
the laser beam direction. This paper indicated that such an off-
axis assembly was easy to implement but difficult to align,
especially if the focal distance changed. This group proposed to
overcome this problem by using a collinear arrangement difficult
to realize due to the large range of optical wavelengths
encountered (IR for the laser and UV to visible for the plasma
emission). It tested a novel setup where the laser axis was
collinear to the path of plasma light collection eliminating the
problem of parallax as the sample distance changed. For this
task, a fully achromatic beam separator based on the principle of
frustrated total internal reflection was inserted between the laser
and the Galilean telescope used both for focusing of the laser
beam onto the sample surface and for collection of the returning
plasma light.
This setup was one example of collinear arrangement where
the plasma light is diverted from the laser path by a beam splitter
which not efficiently reflects all spectral regions. To avoid this
problem, a quartz plate beam splitter was inserted in [48]
between the laser and the beam expander used for laser focusing
and plasma collection, to divert with intensity attenuation, a
fraction of the plasma light to the optical fiber that carried the
signal to the spectrograph. Loss of returning plasma light was
also encountered in [33,35–38,40,41,43–45,55–57] where an
aluminized mirror with a large central clear aperture reflected
the plasma light. The authors of [33,55–57] notified that one
disadvantage of an aluminized folding mirror is to limit the
incident laser pulse energy to below the optical damage
threshold of the coating. In these works, the plasma radiation
folded via the aluminized mirror was gathered with a Newtonian
telescope (40 cm diameter) placed coaxially with the refractive
telescope used to expand and focus the laser beam, and was then
focused onto an optical fiber (600 μm core diameter) connected
to a spectrometer. In [35,40,41,43–45], a Newtonian telescope
(f/4 and primary mirror of 200 mm diameter) was also chosen
for collection of the plasma light diverted from the laser path by
the pierced mirror. In [35,40,41], the image of the plasma
produced by the telescope (Fig. 1) was directly realized on
the entrance slit of the spectrograph (f/3.8, 0.275 m) while in
750 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
[43–45], it was positioned on an optical fiber whose end was
imaged on the entrance slit of the spectrograph with a couple of
plano-convex lenses. The principal difference between these
two arrangements was the light throughput to the spectrograph.
In [36–38], the plasma light guided via the pierced mirror
(Fig. 2) was imaged by a simple lens on a fiber optic bundle
consisting of 50 fibers (100 μm core diameter, 12 m length) and
at the output, a line arrangement of the fibers was connected to
the entrance slit of the spectrometer (f = 0.5 m) equipped with a
photodiode array detector.
While these configurations used an optical system that
passed the laser beam but reflected the plasma wavelengths,
Palanco et al. in [66] employed the converse arrangement
(Fig. 3). They used a dichroic mirror to reflect the laser beam
onto the sample and to transmit the plasma radiation which
directly entered the spectrograph (at approximately f/40,
estimated from the diameter and distance to the focusing
mirror) while, in [66,67] (Fig. 4) it was focused into a fiber optic
cable (600 μm core, 2 m length) connected to the spectrograph
slit with an aperture ratio close to the f/10 of the primary mirror
of the Herschelian telescope. In [42], they also used a dichroic
mirror for separation of laser beam and returning plasma
light which was directly focused to a Newtonian telescope (f/4,
200 mm diameter primary mirror) and then to the entrance slit of
the spectrograph. The ChemCam instrument in development for
Mars exploration [30] will use a dichroic mirror to separate the
laser beam from the plasma light which will be collected by the
Schmidt–Cassegrain telescope and focused onto an optical fiber
connected to the spectrographs.
The intensity attenuation induced by the coating of the
dichroic mirror in some spectral regions was shown for example
in [67]: the LIBS spectrum of a Ti standard sample acquired at
30 m by using a dichroic mirror and a lens to focus the plasma
light onto a fiber optic was compared to a LIBS spectrum
acquired locally at approximately the same laser irradiance but
using the optical fiber as the only collection element.
Comparison of the two spectra illustrated that the performance
of the stand-off LIBS instrument decreased in the UV, with zero
transmission at 350–370 nm and below 300 nm, regions of
lower transmittance of the dichroic mirror. The dip at 355 nm
coincided with the third harmonic of the fundamental Nd:YAG
radiation for which mirror reflectance was designed to be a
maximum. To avoid this problem, Sallé et al. [50,58] replaced
the dichroic mirror by a quartz plate at 45° allowing both
transmission of all plasma wavelengths and reduction of laser
energy on the sample. The use of the quartz plate was possible
because the output laser energy of 700 mJ was high enough to
reach 25–30 mJ on the target, similar to that considered
achievable by a compact laser to be utilized in the envisaged
space application. As the plasma light was collected and
focused onto an optical fiber by a lens, chromatic aberration
existed in this setup and the fiber optic was positioned to give
the optimal signal across the largest part of the Echelle spectral
window. A lens (25 mm focal length) was also employed to
focus the plasma light into an optical fiber connected to a
spectrograph in the telescope LIBS instrument presented in
[59–65]. As the collection angle is limited by the diameter of
the collection lens, the experimental setup described in
[22,46,47,49,51] utilized a lens of larger diameter (100 mm)
than the transmitting dichroic mirror to collect and focus a
greater amount of returning plasma light onto the optical fiber.
3.1.4. Spectrograph and detection systems
The most common optical spectrographs used for stand-off
LIBS analyses were of the Czerny-Turner configuration. In
some works [3,22,37,46,54,69–71], they were equipped with an
intensified photodiode array detector but in the majority of
studies, they were coupled with an Intensified Charge Coupled
Device (ICCD) [35,22,39–48,50,52,53,61,66–68,70]. These
last detectors are preferred for low light level detection that may
be encountered for LIBS analyses at long distances, because of
their lower dark current. Time-gated detection of the laser
plasma can be realized by electronically control the intensifier
(e.g. micro-channel plate) of the ICCD. Several papers have
also reported stand-off LIBS results obtained with Echelle
spectrograph equipped with ICCD detector [34,47,49–
51,58,67] with the advantage of recording a broad-band
spectrum (typically 200–900 nm) in high resolution. New
designs of very compact Czerny-Turner spectrograph incorpo-
rating CCD array detectors have been developed for LIBS.
Several spectrometers can be stacked together to monitor
simultaneously different spectral ranges. This kind of spectro-
graphs have been tested principally for stand-off LIBS applied
to space exploration at reduced pressure where minimum size
and mass is needed [30,49,52] and for commercial develop-
ments [61]. As these devices have no intensified detectors,
temporal delay of the plasma light emission cannot be achieved
in the usual way through gating of the intensifier.
3.2. Applications
Stand-off LIBS with nanosecond pulses has been used
mainly for the analysis of solid samples with ranges up to 100 m
for applications in industrial process control, nuclear power
stations, environment survey, planetary exploration and cultural
heritage. Metal samples have generally been used to demon-
strate the feasibility of stand-off LIBS analysis with the systems
developed by the different research groups. Liquid and molten
samples have been studied at distances of a few meters. The
analysis of gases at long distances has not been reported using
stand-off LIBS with nanosecond pulses due to the high-power
density required to induce gas breakdown.
3.2.1. Industrial applications
3.2.1.1. Industrial process control. The quality of a finished
product largely depends on the possibility of having represen-
tative feedback in different fabrication stages. The analytical
control of the pre-product along the fabrication process is
essential, from the first treatments to the finished product. In the
steel producing industry, conventional analysis methods entail
an excessive time cost, since they require taking a sample from
the melt, transport to a laboratory, sample preparation and
analysis. When analyzing liquid steel, sampling entails a serious
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
risk to the operator. A significant reduction of the time
necessary to gain information about the composition of the
melt can be achieved by directly analyzing the liquid metal.
LIBS combines several advantages for on-line process control
since it can provide composition information in real-time
without sample preparation and with the possibility of stand-off
measurements. Improved steel qualities are a demanding task
for this industry. For example, concentrations below 10 ppm of
sulfur and phosphorus are required to achieve the desired
material properties of the pre-products. The composition of a
steel melt is influenced by chemical reactions of the melt with
the slag components. Therefore the chemical analysis of the slag
provides information on an efficient metallurgical process
control. The major difficulty is to have access to the melt with a
system allowing effective transmission of the favored analytical
emission lines of C, S and P in the short ultraviolet wavelength
range (no possible use of fiber optic). Concerning stainless steel,
a high-technology material with a diverse range of compositions
and mechanical properties, the addition of Cr in high
concentration (over 10%) introduces excellent resistance to
corrosion. In the presence of oxygen and at high or moderate
temperature, stainless steels lose their protective oxide layer and
experience superficial oxidation (scaling process). The result is
the growing of a thin layer composed of a mixture of Fe and Cr
oxides in variable proportion and thickness depending on steel
composition, sample temperature, environmental conditions
(mainly humidity) and exposure time. The LIBS signal from a
number of subsequent pulses on the same sample location will
provide information about compositional changes along the
sample thickness.
One of the first reports of metal analysis at a distance using
LIBS was published in 1987 by Cremers [3] with the goal of
demonstrating the possibility of performing LIBS analysis at
distances between 0.5 and 2.4 m, and the rapid sorting of
different metals. The results principally obtained for a lens to
sample distance of 55 cm and for direct plasma light collection
by a fiber optic cable, showed 100% success at the identification
of metals according to their main constituents. They also
demonstrated the identification of surface contamination by
repetitive ablation. The plasma signal induced at a distance of
2.41 m from the lens by a 227 mJ laser pulse and focused onto
the fiber optic with a lens of 5 cm focal length allowed preparing
a calibration curve for Mn in steel with concentrations between
0.047 and 1.38% with a correlation coefficient of 0.993.
In 2002, Palanco et al. [39] used an open-path LIBS system
with a laser energy of 230 mJ and a collection distance up to
45 m to analyze stainless steel samples at room temperature,
outline the feasibility of this approach and take a first step
toward the investigation of its potential. The Cr emission signal
at 540.97 nm was studied as a function of the distance from the
focusing lens to the sample between 35 and 45 m. The absolute
signal RSD (Relative Standard Deviation) was found to be 14%
as the sample position varied of ± 1 m from the position of
the optimum laser focus. However, the Cr signal normalized to
the Fe matrix emission intensity had a steady behavior along the
whole 10 m lens to sample distance range, showing that
the effect of surface irregularities was minimized in stand-off
751
analysis. Spectra from six stainless steel samples were
compared to reference spectra of Nb, Ti, Mo and Ni indicating
several emission lines which allowed the identification of the
six steel grades. These data were used to design a three-
dimensional pattern-recognition algorithm in which Ni, Mo and
Ti were in the axes. Despite the low precision, signals corres-
ponding to similar sample concentrations produced well-
defined groups which enabled to successfully classify the six
steels at 45 m.
In 2003, Vadillo et al. [35] checked the performance of their
LIBS remote system by monitoring the Al resonant lines at
394.40 nm and 396.15 nm from an aluminum sample placed at a
distance of about 6 m from the laser which delivered an energy of
250 mJ (32 J/cm2). The plasma light collection was performed
for three different optical path lengths (25, 80 and 100 m). A 16
fold decrease in the intensity collected at 100 m when compared
to the signal measured at 25 m was attributed to the theoretical
inverse quadratic dependence of the collected signal with the
distance. The good signal to noise ratio observed for the three
collection distances showed the possibility of collecting light
emission from plasmas at distances between 25 and 100 m. The
Al spectrum collected at 100 m at room temperature with a laser
energy of 390 mJ showed lower emission intensity and signal to
noise ratio than those observed on a spectrum obtained when the
Al sample was placed inside a laboratory oven at about 600 °C.
The authors also collected spectra of stainless steels at a distance
of 12 m when the samples were placed into the oven at about
1200 °C and 12 m away from the laser. This temperature was
chosen because chromium scales are able to provide sufficient
corrosion or/and oxidation protection exclusively at low to
moderate temperatures, up to about 900 °C. The evolution of the
intensity of the Cr line at 540.98 nm as a function of the number
of laser shot evidenced the alteration layer on the steel matrix and
showed the possibility of performing dynamic studies of
elemental migration at high temperature in alloy steel samples
placed remotely.
Palanco et al. [40] described in 2004 the construction of an
open-path LIBS analysis system where the plasma light was
collected along the same path as the laser beam. Performance of
the system was evaluated by comparing spectra of an aluminum
standard sample obtained at 10 m under a remote open-path
configuration with a laser energy of 820 mJ and at 25 cm using a
conventional setup with similar irradiance and collection
conditions (solid angle). Comparable signal to background
ratios for the 396.15 nm Al line (1902 for the open-path
configuration compared to 1876 for the local configuration)
illustrated the possibility of using the open-path LIBS system
proposed as compared to a conventional LIBS setup. Improve-
ment of the signal to noise ratio was possible by increasing the
averaged number of pulses, since the Al signal to noise ratio
increased with the number of averaged spectra and it depended
of the square root of the photon number on the detector until
about 100 averaged spectra (photon noise limitation). To verify
that the performance of the instrument degraded as the solid
angle of collected plasma light decreased with the square of the
working range r, the Al signal to noise ratio obtained from 100
averaged spectra was plotted versus the working distance
752 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
(between 5 and 100 m). The experimental signal to noise ratio
data fitted to a function 1/r1.1 and this power dependence was
quite close to the theoretical value of 1/r expected under shot
noise limited conditions. Extrapolation of this fitting to signal to
noise ratio of 3 yielded a maximum collection range of
approximately 950 m. It must be noted that the resonant nature
of the Al line used in this study might lead to enhanced results
and a decrease in the maximum workable range might be
foreseeable with other samples.
The same group [66] presented the same year an open-path
LIBS instrument to explore certain aspects of the quality control
of molten stainless steel with a series of tests realized under
controlled conditions in a laboratory induction furnace of 1 kg
capacity, necessary step previous to the validation of the
technique on an industrial scale. Spectra of stainless steel
samples acquired at 7.5 m at room temperature and at 1420 °C
before the melting point showed that the emission intensity of
all analyzed species Fe, Cr, Ni, Mn increased at high
temperature. The plasma temperature, calculated from the
Boltzmann plot method, increased with the sample temperature
showing that the higher plasma temperature was at least partly
responsible for the intensity increase. An increase of the
ablation rate at high temperature could also contribute to the
intensity raise. The spectra of the same samples obtained at
1420 °C just before melting and just after melting showed that
in addition to the overall intensity increase, the spectrum
corresponding to the molten steel revealed the presence of
several spectral features which were absent in the spectrum
corresponding to solid steel. These lines were assigned to Ti,
Mn and Cr, which at high temperature were oxidized under a
non-inert atmosphere, resulting in the formation on the sample
surface of a scale layer enriched in these elements. With the aim
of assessing the technology for the on-line elemental analysis of
molten steels, calibration curves for Ni and Cr were prepared by
adding these elements to liquid steel. The limits of detection for
Ni and Cr were estimated to be 540 and 1190 ppm respectively
with RSD of 1.83 and 2.05%, acceptable for the application
under study. The instrument was successfully installed in the
stainless steel factory and LIBS evidenced the capability to
reveal surface composition changes on-line, and with real-time
at very high temperatures.
Other experiments were conducted by the same group in the
laboratory with the steel samples maintained in an oven with
temperatures ranging from 20 °C to 1200 °C at a distance of
10 m from the laser source [41]. Spectra acquired as a function
of the number of laser shots showed that after 10 min exposure
at 1200 °C, the scaled layer was Fe-rich with reduced levels of
Cr, Ni, and Mo compared with the non-altered steel matrix.
These experimental results confirmed the possibility of stand-
off LIBS to monitor the corrosion of stainless steels in a high-
temperature environment.
In 2005 [44], Lopez-Moreno et al. proposed a method for
remote LIBS quantitative analysis of samples at high temperature.
They proposed to use a transfer function which allowed obtaining
the composition of the sample at high temperature using a
calibration curve performed with standards at room temperature,
thus avoiding the need to perform calibration curves at high
temperature. Spectra of steel slag samples at room temperature
were acquired at 12 m from the remote LIBS instrument. The
analysis conditions were optimized for the slag samples resulting
in 50 preparation shots followed by 50 averaged spectra with 5
replicates for each sample. Calibration curves were prepared for
Si (288.16 nm) and Mg (279.55 nm) both normalized to Ca
(300.68 nm) and detection limits of 0.437 and 0.005% were
determined respectively for the two elements. For high-
temperature measurements, the authors proposed to use a transfer
function to transform the intensity of the element of interest at
high temperature into its corresponding value at room temperature
via the calibration curves realized at room temperature. The
method was shown suitable for high-temperature measurements
up to 850 °C in steel slag samples and its accuracy was
demonstrated by the good correlation between the relative
concentrations or the basicity index (a measure of the desulfuri-
zing and dephosphorizing power of the slag) obtained with stand-
off LIBS at high temperature and those of XRF at room
temperature. The suitability of the transfer method was also
demonstrated the same year [45] for the composition determina-
tion of eight stainless steel samples placed at 12 m from the remote
LIBS instrument. A relative error lower than 16%, 21% and 6%
was obtained between respectively the Mn, Ni and Cr concentra-
tions determined at 1000 °C using the transfer method and those
calculated from calibration curves prepared at room temperature
with the same samples.
In 2006, Palanco et al. [67] described the design of a
completely new concept for a field-deployable instrument
capable of performing stand-off LIBS measurements in the
hundreds of meters range with the use of a Herschelian
telescope for laser focusing and plasma light collection. As in
their previous works, they evaluated the performance of their
system by studying the LIBS signal (averaged over 100 laser
shots) of the 396.15 nm Al line from an aluminum sample as a
function of the analysis range from 25 to 95 m. The LIBS signal
strongly decreased with the analysis range but conversely with
previous results [40], the data did not fit to an inverse square
function, evidencing that plasma conditions were changing with
analysis distance. The signal decrease corresponded to the great
decrease of mass removal with decreasing laser irradiance or
increasing analysis distance. It was more generally shown that
LIBS performance at stand-off distance depended on several
parameters such as analysis range, peak power, beam quality,
laser wavelength and dimensions of the optical element used to
transport the laser beam. The study of Ti, H, O and N emissions
versus the distance from a Ti sample to the focus of the
instrument showed that the interaction of the plasma with the
surrounding atmosphere favored by the long depth of focus
related to stand-off configurations could induce laser beam
defocusing and shielding.
In real industrial conditions, the mobility of the sample could
require analysis of the sample at incidence angles other than
normal or the target morphology could yield different incidence
angles. That is why the same team investigated in 2007 how the
movement of a stainless steel sample affected the LIBS emission
signal at different angles of laser incidence for a stand-off
distance of 10 m [42]. The Cr emission intensity was observed
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
decreasing for increasing target speed up to 24 cm min− 1, in
relation with the amount of sample surface overlapped by
successive laser shots and this could be controlled by changing
the laser repetition rate for a given sample speed. For laser
incidence angles below 40°, the signal was not significantly
influenced by changes of the incidence angle but decreased with
increasing angle above 40°. Under simulated field conditions
(10 m from the laser, incidence-collection angle of 40°, 24 cm
min− 1 target speed), a pattern-recognition space with Ni, Ti and
Mo signals as three variables allowed accurate sorting of five
different steel grades, demonstrating the suitability of the stand-
off LIBS technique for semi-quantitative analysis.
Gruber et al. also reported analysis of metal melts by LIBS
for process control in metallurgy [36–38]. The real-time
monitoring of Cr, Cu, Mn, and Ni contents added in variable
concentrations to a liquid steel bath placed in a laboratory
induction furnace was demonstrated at a distance of 1.5 m [38].
A good correlation between the relative contents of Cr, Mn and
Ni measured by LIBS and standard laboratory analyses for 12
different stainless steel heats was also obtained in a vacuum
degassing vessel at a pressure of about 1 mbar with a flushing of
Ar or N2 at a distance of 4 m from the focusing mirror [37].
Monitoring of the chemical composition of a Ni alloy placed at
2.5 m from the LIBS instrument in a vacuum induction melting
furnace at a pressure of around 0.2 mbar Ar was demonstrated
by plotting the evolution of Cr and Ti emission lines before and
after addition of an alloying substance containing Ti to the
liquid metal bath.
The performance of a customized mobile LIBS system was
tested during a field campaign for in-situ and on-line process
analysis of major components of a mineral melt at 1600 °C for the
production of mineral wool [34]. Pulse irradiance (6.5 GW/cm2),
gate delay (1.3 μs) and width (1 μs) of the ICCD detector, and
distance from the laser to the melt were optimized in term of signal
to noise ratio. This permitted all major elements in the melt
(Ti, Fe, Mn, Mg, Ca, Si, Na and Al) to be identified from a
spectrum corresponding to ten laser shots. For process monito-
ring, LIBS measurements from a melt were made at analysis
intervals separated by 60 s of manual retrieval of a sample from
the melt for subsequent XRF analysis utilized for reference
analysis. Results from two different measurements sampled for
80 and 130 min were compared and reasonable correlation was
observed between the LIBS intensities and XRF data for major
changes of the Si, Fe, Al, Ca, Mn, Mg elemental concentrations.
The temporal resolution of the LIBS technique was superior to
that of manual sampling and XRF analysis, and this could be
helpful for on-line process control but also for determining
dynamic processes in the melt.
3.2.1.2. Applications within the nuclear industry. Composi-
tional analysis of highly radioactive materials generally requires
specialized equipment and facilities for the removal, transport
and chemical analysis of the samples. Non-contact stand-off
LIBS is particularly attractive within radioactive environments
because measurements offer significant savings in cost and time
compared to conventional analytical methods, and also avoids
the risk for secondary waste.
753
The first use of a telescope LIBS instrument to remotely
analyze the composition of contaminants deposited on dissolver
baskets at a spent nuclear fuel reprocessing plant was carried out
in 2001 [59,62–65,71,72]. Radiometric analysis of the
contaminants had identified the radionuclide components but
another method was needed to obtain information on the non-
radioactive materials. A transportable telescopic LIBS instru-
ment was deployed to form the laser plasma at a distance of
about 5 m of the steel basket and to collect the plasma light via a
1-m thick lead-glass radiation shield window of a hot-cell. The
optical properties of this shield window limited the range over
which the plasma emission could be monitored to wavelengths
higher than about 500 nm. Kinetic series of spectra recorded
with laser pulses of 350 mJ suggested that the contaminant
material was rich in Zr and Mo. By combining this information
with existing knowledge of the process chemistry, it was
deduced that the contaminant material consisted mainly of
zirconium molybdate, a material known to form during the
reprocessing of spent fuel and largely insoluble in nitric acid.
The LIBSCAN instrument [61] was deployed to remotely
detect fixed contamination on the surface of high-level waste
containers [72] by using the method patented in [73]. Indeed,
the preferred method of processing high-level waste is
vitrification whereby the radioactive material is incorporated
in a glass or ceramic matrix to produce a very chemically stable
material suitable for long-term storage. After the containers
have been filled with waste, they are decontaminated and then
the external surfaces are monitored for residual contamination
by using a robotic swabbing technique and radiometric
monitoring of the swab. This last monitoring system may not
detect the fixed contamination which corresponds to small
quantities of vitrified product arising from splashing during the
filling process and that may strongly adhere to the outside walls
of the containers. The LIBS instrument provided a comple-
mentary monitoring technique to robotic swabbing by detecting
the matrix material (glass or ceramic) on the outsides of
containers (such as stainless steel drums). It was placed outside
the hot-cell (only the steering mirror and focusing lens were
exposed to the nuclear radiation) and incorporated a ‘through-
wall’ optical endoscope which was an optical-quality quartz
light guide commonly used throughout the nuclear industry.
Spectra obtained from this LIBS instrument exhibited emission
lines characteristic of Na and Li, elements contained at high
concentrations in glass matrix, thus showing the possibility of
reliable and sensitive detection of fixed contamination on the
containers.
A telescope LIBS instrument was also used to identify
reinforcing bars and cooling-water tubes within the concrete
pressure vessel of a Magnox reactor [60,63,72]. During a
maintenance and repair program at the nuclear power station,
there was a requirement to drill a large number of bore-holes
into the steel-reinforced concrete pressure vessels of the two
reactors for a reinforcing structure being added. In the concrete
structure were embedded cooling-water tubes to maintain the
temperature of the concrete within certain limits and it was
imperative not to damage these cooling-water tubes when
drilling the bore-holes. A method was necessary to stop the
754 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
drilling process automatically in the event of contact with a
metallic object and a LIBS instrument was proposed to
distinguish the composition between a cooling-water tube and
a reinforcing bar. The measurement precision of this LIBS
instrument was sufficient to resolve known differences in
composition between the cooling-water tubes containing less
than 0.8% Mn and the reinforcing bars containing approxi-
mately 1.5% Mn.
3.2.2. Detection of contamination in insulator systems
A general threat to the insulation properties of high-voltage
insulator systems is surface contamination such as salt. It is
important to find reliable methods to detect such contamination
in order to apply a cleaning process which is vital for a reliable
transmission of electric power. LIBS was used for detection of
contamination in high-voltage insulator systems and was
performed on both types of surfaces contained in such systems,
i.e. the electrode material copper and the insulator material
silicon rubber. When LIBS (LIBS lidar system, spot diameter at
the target around 5 mm) was applied to a salt-covered copper
plate in motion placed at a distance of 60 m, the Na line at about
589 nm, characteristic of the salt, was observed [57]. When
LIBS was performed in the same experimental conditions on a
salt-covered silicone rubber surface, the fluence was too low to
create a breakdown. To produce a plasma onto the salt-covered
insulator target with clear Na emission, it was necessary to use a
collimated laser beam (LIF Laser-Induced Fluorescence lidar
system) and to insert a lens into the beam path to focus the laser
onto the target with a spot diameter of 0.7 mm. The additional
lens not only increased the laser intensity at the target but also
collected more plasma light back to the detection system.
Ablative cleaning of an insulator surface was also performed by
using LIBS by controlling on LIBS spectra the disappearance of
the Na line with the number of laser shot increase.
3.2.3. Environmental control
In 2004, remote LIBS was demonstrated as a valuable
analytical tool for both qualitative inspection and quantitative
determinations on environmental samples from a coastal
scenario subjected to high industrial activity [43]. All the
LIBS measurements were carried out in the laboratory on
samples including soils, rocks and vegetation placed at a stand-
off distance of 12 m from the spectrometer. Depth profiles of a
dock rock sample showed that Cr and Fe emissions were clearly
more intense in the surface than in the sample matrix evidencing
for the presence of a contamination layer on the sample surface.
Detection limits for Cr and Fe were determined to be about 0.2%
from calibration curves prepared using slag samples as
standards. These curves were then used to estimate the amount
of Cr contained in the dust deposited on some of the collected
samples. Among the main factors influencing the analytical
results, sample moisture and salinity, sample orientation and
surface heterogeneity were identified. The changes in Cr signals
(concentrations) with laser shot number on the different samples
were used to draw conclusions regarding aspects of environ-
mental pollution. The presence of Cr in the surface of bark and
leave was significant in the layer removed by the first pulses
evidencing the ability of vegetation to trap and retain surface
contamination. The intense Cr signal observed on the whole
thickness of the soil sample was indicative of the high diffusivity
of contaminants through this kind of porous and granulated
samples. The continuous cleaning and erosion of the surface of a
dock rock by the sea water and the high porosity of the surface
were found the main reasons for the lower Cr concentration in
the surface and the thicker contaminated layer than the other
samples. Stone and fragment of wall taken close to a factory
revealed a higher Cr signal in the first layers, probably due to the
proximity of these samples to the contamination source. The
heterogeneity of environmental samples is one of the main
drawbacks to achieve representative analytical results with
LIBS. For this reason and using the large depth of focus of the
optical system at 12 m, an area of 20 × 18 mm was scanned across
the surface of a dock rock and in 0.54 mm depth to obtain a three-
dimensional map of Cr, Fe, Ca and Mg composition distribu-
tions. The Cr and Fe concentrations decreased in depth
indicating the high degree of contamination deposited in the
sample surface. Ca intensity decreased in depth as well, but
steeply for the first laser pulses due to the higher concentration of
this element on the sample surface. The increase of Mg signal
during the first shots showed the lower concentration of this
element in the polluted layer relative to the matrix.
3.2.4. Planetary exploration
Stand-off LIBS presents many advantages for planetary
exploration compared with past and current methods of elemental
analysis deployed on spacecraft, including rapid analysis, no
sample preparation as scraping or abrasion, ability to be combined
with other optical spectroscopic techniques (Raman, fluores-
cence) that provide data complementary to LIBS. It can also
remove dust layers remotely and perform depth profiles through
weathering coatings and thus provide analyses of the pristine rock
samples. The fact that LIBS can analyze samples at a distance
increases greatly the number of measurements that can be carried
out during the limited lifetime of a mission, compared to contact
or in-situ techniques that can require hours to position the rover
adjacent to the sample. Several studies have reported the
feasibility of LIBS for space exploration with the aim at providing
rock and soil analysis on planet surfaces. They have demonstrated
the capabilities of LIBS for analysis at close and stand-off
distances for atmospheric pressures and compositions simulating
Mars (7 Torr CO2), Venus (90 atm CO2) and the Moon (about
10− 9 Torr).
In 1992 [74], remote LIBS detection of geological samples
was demonstrated outdoors in air by loading a laboratory
equipment onto a movable cart rolling into a parking area
surrounded by a bank of volcanic tuff about 2.5 m high with the
goal of promoting LIBS as an instrument for future planetary
missions. The distance from the cart to the bank was increased
to determine the maximum distance where useful LIBS spectra
could be obtained with laser energy of 320 mJ and it was
measured to be 24 m. In a second test field, the LIBS equipment
was considerably down-sized (use of a diode-pumped Nd:YAG
laser), mounted on a breadboard and tested by recording spectra
from selected rock samples at distances up to 10 m.
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
In 1995, the same group [46] performed laboratory
measurements to determine the ability of LIBS to provide
useful analytical information at a distance of 10.5 m with
simulants of rocks from the Apollo 11 moon mission in a
vacuum to simulate an extraterrestrial environment. The spectra
obtained with a laser energy of 500 mJ demonstrated that stand-
off LIBS had sufficient sensitivity to detect the Si, Ti, Al, Fe,
Mg, Mn, Ca, Na, K, P and Cr elements of interest to lunar
geologists at concentrations in the moon rock simulant.
In 1999 [22,70], the same LIBS system was used with a
moderate laser energy (40 to 100 mJ) to characterize the stand-
off LIBS analysis of soils at reduced air pressure and in a
simulated Martian atmosphere (5–7 Torr pressure of CO2) to
show the feasibility of LIBS for planetary exploration. The
number of laser shots (80 mJ) necessary to remove a sea sand
layer of 1, 2 and 3 mm thickness deposited on a synthetic
silicate sample placed in 5 Torr CO2 at 19 m was demonstrated
to be 4, 14 and 28 respectively. This was determined by noting
the shot number on which the Sr signal appeared as the sea sand
layer did not contain this element at detectable concentration
contrary to the silicate sample. Detection limits for minor
elements were determined by constructing a calibration curve
for each element using synthetic silicate soil samples in an
atmosphere of 5 Torr CO2. They increased on average by a
factor of 5 as the lens to sample distance increased from 175 mm
to 19 m for a given laser energy of 100 mJ. The authors
attributed this observation to the power density decrease at the
greater distance. The % RSD calculated from 30 distinct
measurements for each element was comprised between 2.5 and
27% depending on the element, and remained approximately
the same for the two analysis distances. In changing the
atmosphere from 5 Torr argon to the same pressure of CO2, the
O signal from soil approximately doubled and the C signal
appeared. This indicated a significant contribution of the
atmosphere in the emission signals, complicating the measure-
ment of oxygen and carbon in rocks and soils, two elements of
geological interest, in presence of CO2 under Martian condi-
tions. Finally, analytically useful spectra could be generated on
a soil sample placed at 19 m in a chamber at 7 Torr CO2 by using
a compact Nd:YAG laser (25 × 25 × 150 mm, 6 ns, 35 mJ),
validating construction of a LIBS instrument with small size.
The analysis of stratified layers of ice and dusts on Mars is
important for understanding the climate and geologic history of
the planet and perhaps even for determining the current or past
presence of life. For this reason, Arp et al. [47] evaluated in
2004 the stand-off LIBS technique to analyze water ice and
water ice/soil mixtures under Mars atmospheric conditions at 4
and 6.5 m defined as the distance from the sample to the plasma
light collection lens. Calibration curves for ice/soil mixtures
were prepared at these stand-off distances using 100 mJ pulse
energy and 7 Torr CO2, and detection limits for Ba, Li, Mn, Sr
and Ti were deduced between 1 and 520 ppm depending on the
element and the analysis distance. The detection limits obtained
at 4 m for ice/10% soil mixtures were comparable to those
obtained by analyzing dry soil samples at 19 m and presented in
[22]. It was more difficult to form analytically useful plasma on
an ice or ice/soil mixture than on a dry soil leading to attainable
755
stand-off distances less important using ice or ice/soil mixtures
than using dry soils.
With the same objective of installing a LIBS system on a
rover for stand-off detection of geological samples on the
surface of Mars, Sallé et al. [50] tested in 2004 the capabilities
of two different laboratory setups dedicated to the analysis of
metals and rocks at stand-off distances in Martian atmospheric
conditions. Exploitable spectra of aluminum and basalt samples
under 9 mbar of Martian gas were obtained for lens to target
distances between 3 and 12 m with laser energy of 31 mJ,
considered in the energy range achievable by a compact laser
likely to be incorporated on a rover. In these experimental
conditions and for an analysis distance of 3 m, calibration
curves for Cr, Mg and Si contained in aluminum alloys were
established. Detection limits between 7 and 74 ppm were
deduced, very close to those reported in the literature for more
standard LIBS setups (e.g. close distance, atmospheric pressure
in air). It was also demonstrated that in Martian conditions, the
detection of Cl and S, two essential elements for studying Mars
surface geochemistry, could be obtained via ionic lines in
spectral regions easier to use with ICCD detectors than atomic
lines usually observed at atmospheric pressure in the IR region.
In 2004 December, the work of this international team
resulted in the selection of a new type of remote-sensing
instrument for the mobile NASA Mars Science Laboratory
(MSL) rover [31,32], scheduled for launch in 2009 to
investigate the Martian geochemistry. This instrument, named
ChemCam, was described for the first time in [30] with its
science objectives in a companion paper [75]. It will consist of a
LIBS analyzer and a micro-imager to provide elemental analysis
at distances from 2 to 9 m from the rover and simultaneously
context imaging. Laser, imager and telescope will be mounted
on the rover mast while three spectrographs, data processing
unit, power supply and rover interface will be located in the
rover body. Electrical and fiber optic cables will control links
between the mast and the body units. The mast unit will focus
the laser beam onto the Martian rocks, generate laser produced
plasmas and collect plasma light for LIBS analysis and ambient
light for imaging. The body unit will collect plasma light for
spectral analysis, command the whole instrument, exchange
data with the rover and distribute power. The primary objective
of ChemCam is to rapidly characterize rocks and soils (by
removing Mars dust from targets), and to identify samples of
greatest interest for further investigation by contact and
analytical laboratory instruments contained in the rover.
ChemCam is expected to help scientists characterize the
geology of the landing region, investigate planetary processes
relevant to past habitability by analyzing ices or salts or rocks
and soils that have been altered by water, assess the biological
potential of a target environment by identifying possible organic
materials, and check for toxic materials.
In 2005, this team presented an evaluation of one design of
very compact spectrograph/detection systems (Ocean Optics
HR2000) being considered for future installation in the LIBS
apparatus on the Mars rover [49]. Exploitable spectra were
obtained under Martian atmospheric conditions at 5.3 m
(distance between the sample and the lens of plasma light
756 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
collection) with the non-intensified HR2000 device and laser
pulse energy of 40 mJ. This demonstrated that non-intensified
detection was possible for LIBS at 7 Torr CO2 and that the
commercial HR2000 units with different spectral windows had
spectral coverage and resolution sufficient for the detection of
elements of interest to geologist. Calibration curves prepared
using a set of certified soil and stream sediment samples led to
acceptable precision on detection limits (5 to 20% for the
majority of studied elements). For space applications, tests
(thermal, vibrational, radiation) of the HR2000 units are needed
to design a flight-rated version of these devices.
By using the same experimental configuration, Thompson
et al. [51] demonstrated in 2006 that the LIBS technique was
capable of determining subtle differences in rock types placed at
stand-off distance of 5.4 m. They analyzed two Martian basaltic
shergottite meteorites, Dar al Gani 476 and Zagami, with
slightly different compositions, textures and grain sizes as well
as an andesite rock powder standard. Seven basalt powder
standards were also analyzed under simulated Martian condi-
tions (7 Torr CO2) to prepare calibration curves for Fe, Mg, Si,
Ca, Ti, Al, Na and K which served for oxide composition
determination of the two meteorites and the andesite standard.
The differences between LIBS and published laboratory results
differed by less than 12% for most of the major elements
contained in Dar al Gani 476 and 7% for Zagami. The
uncertainty in the LIBS analysis of the andesite composition
was less than 5%. The agreement for Ti and Na was not so good,
due to the low emission signals of these elements present in the
samples at concentrations less than 1%. The better results
obtained for the andesite could be explained by the fact that it
was a powdered sample, homogeneous on the scale of the laser
spot, while the Martian meteorites were slabs of rock and
needed numerous analytical points to obtain a good average
analysis. The LIBS analyses also clearly distinguished between
the two Martian basaltic meteorites in terms of the differences in
the MgO and CaO contents.
In the previous works, LIBS quantitative results were obtained
from calibration curves built with known reference powders
where the major element concentration was constant and only the
minor and trace element concentrations varied. This cannot be
applied when samples of the same rock type with variable
concentrations are not available and this is not compatible with
field analyses of complex and a priori unknown samples as for the
case of soils and sediments that will be encountered on
the Martian surface. That is why Sallé et al. [58] evaluated in
2006 the LIBS response as a function of concentration by
performing multi-matrix calibration curves with several types of
natural standard rocks e.g. volcanic rocks, gabbro and limestone.
The preparation of calibration curves for Si, O, Ca, Fe, Mg, Al,
Na, K, Ti, Ba and Sr at an intermediate stand-off distance of 3 m
and in a simulated Martian atmosphere (9 mbar CO2) highlighted
the matrix effects between the different studied rocks. Therefore,
the authors evaluated three different methodologies for correcting
the matrix effects and for obtaining quantitative results on
inhomogeneous and unknown samples on Mars. Firstly, they used
an external reference sample (trachyte) and normalized to the sum
of all elemental concentrations. Secondly, they used the internal
standardization by oxygen, the major element common to all
matrices, and finally they applied the Calibration-Free LIBS
method [76]. The three evaluated methods clearly demonstrated
that the matrix effects could be corrected by merely taking into
account the difference in the amount of vaporized atoms between
the rocks, no significant variation in plasma excitation tempera-
tures being observed. These three methodologies allowed
concentrations to be determined with accuracies compatible
with the ChemCam requirements (10% for the major elements).
The study performed on the instrumental noise levels highlighted
that high RSD values associated with low emission signals
collected with an Echelle spectrometer equipped with an ICCD
camera was the main limitation on the distance at which
quantitative analyses could be performed.
One advantage of the LIBS technique is to be readily
combined with other spectroscopic methods that use essentially
the same instrumentation and have stand-off analysis capability.
The May 2000 Field Integrated Design and Operations (FIDO)
and the K9 Mars prototype rover field trials near Black Rock
Summit, Nevada, was the first occasion during which a compact
LIBS instrument was integrated onto a NASA rover to evaluate
qualitative analysis capabilities, such as rock identification, and
compare with reflectance spectroscopy [48]. The LIBS field
prototype was installed on the mast-head and a fiber optic cable
carried the collected plasma light to the spectrograph and detector
placed in the body of the rover. The effective working range of the
LIBS instrument was 2–6 m. LIBS results obtained on 14 rock
samples collected from the field site were qualitatively compared
to the spectra realized on 16 rock powder standards in laboratory
under the same conditions as the rocks. The authors indicated that
quantitative results could not be given with the employed setup
because of, firstly, the large range of compositions encountered at
the investigated site (a great number of standards were needed for
calibration), and secondly, the low spectral resolution and limited
spectral range of the current spectrograph (which potentially
allowed interfering peaks to be recognized). While single spot
analyses (∼1 mm size) may not be representative of the bulk rock,
analysis of several spots rapidly converged on an accurate
characterization of the rock. Differences in interpretation between
LIBS and reflectance spectroscopy tended to be due to surface
coatings that LIBS was able to distinguish by depth profile in
contrast to reflectance spectroscopy which reported them as
admixtures with the bulk rock. This work showed the advantages
of combining remote-sensing techniques on rover for rapid
characterization by visual information of rock texture, important
to understand the origin of the studied sample, by mineralogical
information given by reflectance spectroscopy and by determi-
nation of elemental composition by LIBS.
Combination of LIBS with pulsed-laser Raman spectroscopy
was demonstrated in 2002 by Sharma et al. for mineral analysis
on planetary surfaces at distances from 10 to 66 m [77]. Although
the LIBS technique yields information on elemental composi-
tions, the Raman spectroscopy yields information about minerals
and also identifies organic molecules from vibrational spectra.
Combining mineralogical and elemental composition techniques
in a single instrument allows more complete identification of
samples that possible with a single technique. In 2002, Hubble
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
et al. modified their existing stand-off Raman system to collect
LIBS data on mineral samples at a distance of 10 m [53]. They
used two different Nd:YAG laser sources, one operating at
1064 nm and 200 mJ per laser pulse for LIBS and the other
emitting at 532 nm with an energy of 28 mJ for Raman spec-
troscopy. The LIBS spectra of dolomite, magnesite, calcite and
pink coral were used to determine the ratio of Ca to Mg in the
samples while the Raman spectra of dolomite, magnesite and
calcite evidenced the band characteristic of CO32− ions contrary to
the pink coral Raman spectrum. The quantitative information
provided by LIBS combined with the Raman signature of the
anion group will allow identifying and characterizing the compo-
sition and mineralogy of crystals and rocks on planetary surfaces.
In 2005, Wiens at al. used LIBS and Raman spectroscopy at
a stand-off distance of 8.3 m to demonstrate the feasibility of a
synergy between these two techniques in air [52]. The principal
difference between gypsum (CaSO42H2O) and anhydrite
(CaSO4) LIBS spectra was the presence of a hydrogen peak
from the bound water in gypsum. The differences in the Raman
spectra of these two samples reflected the difference in their
crystal structures from the presence and absence of hydrogen
bonding. The dolomite (CaMg(CO3)2) LIBS spectrum was
distinguished from that of the diopside (CaMgSi2O6) thanks to
the Si peaks in diopside, the characteristic C line in dolomite
was below detection under the experimental conditions used in
this work. In the Raman spectrum of dolomite could be easily
identified the carbonate minerals while the bands present in the
Raman diopside spectrum could be used to determine the
presence of pyroxene silicate chains. The LIBS spectra of chalk
and calcite samples appeared identical but the Raman spectrum
of chalk showed a short-lived fluorescence background
identifying it as a calcite polymorph. Apart the strong synergy
between the two measurement techniques, the development of a
combined instrument is supported by the common components
needed for the two techniques: a laser, a telescope if the
investigation is realized at stand-off distances and a spectro-
graph. Challenges concern how to cover the wider spectral
range desirable for LIBS (∼ 650 nm compared to 150 nm for
Raman spectroscopy) with sufficient sensitivity for the Raman
signal (a factor of about 20 difference in intensity was observed
between the brightest Raman line of calcite and the brightest
Ca LIBS emission line, measured for the same laser
parameters). Such combined Raman-LIBS instrument is
planned to be part of the Pasteur instrument payload on the
ExoMars rover mission scheduled by the European Space
Agency for a 2011 launch [78,79].
3.2.5. Detection of explosive residues
A suitable analytical technique should be able to differentiate
energetic materials from innocuous substances with a reaso-
nable level of confidence. Remote analytical techniques like
LIBS are the only ones that offer real-time analysis maintaining
a security distance from the sample and avoiding risks for
the operator. In 2006, Lopez-Moreno et al. [68] used an open-
path LIBS system working under a coaxial configuration to
demonstrate the feasibility of detecting energetic materials
which are commonly organic compounds, at distances up to
757
45 m with laser energy of 350 mJ. Although they mainly chose
to analyze energetic materials of military use, their work was led
in the framework of an investigation on the capabilities of LIBS
for the stand-off detection of explosive residues in the field. The
presence of the C2 Swan band at 516 nm in the spectrum was
used to discriminate organic samples from inorganic ones. An
algorithm based on the observation of the C2 band, the H, N, O
elements in combination with a peak intensity ratio analysis
(H/C2, O/H, O/K, O/N and Na/C2) was developed to allow
classification of the samples as non-organics, organic non-
explosives and organic explosives. The suitability of the data
processing was demonstrated in the field by identifying 13 out
of 15 known samples and also 6 out of 6 unknown samples
deposited on the door of a vehicle located at a distance of 30 m
from the LIBS instrument. The detection of energetic materials
in one fingerprint or one 100 ppm solution drop containing
about 5 μg of explosive was considered as a satisfactory limit
of detection at a distance of 30 m.
3.2.6. Cleaning of objects of cultural heritage
In the past ten years, LIBS has emerged as a very promising
technique for the analysis and characterization of a broad variety
of objects of cultural heritage including painted artworks, icons,
polychromes, pottery, sculpture, metal, glass, and stone objects.
Laser ablation is used for surface cleaning of environmental
deposits on stone or marble or corrosion products on metal
surfaces, and LIBS can provide spectral differences between the
removed surface layer and the art object. The remote-imaging
LIBS and remote ablative cleaning of stone surfaces were
described for the first time in 2005 by Grönlund et al. [55]. By
scanning the laser beam of a mobile lidar system under computer
control, it was possible to generate LIBS imaging of metal plates
(copper, stainless steel, brass, aluminum and iron) placed on an
easily accessible roof at about 60 m from the system, by looking
at the characteristic lines of the different elements. Oxide layers
could be removed from metal targets. Even the green copper
hydroxide typical of copper roofs could be ablated, and spectral
differences could be noted as the surface was cleaned. The same
setup was also used to demonstrate laser cleaning of stone
surfaces at 60 m: — biodeteriogen layers were removed from
mortar surfaces and granite rocks, — pencil and marker-pen
blackened areas were removed from white alabaster slabs, — a
1 m tall white Italian garden replica statue was cleaned of dirt and
algal growth after ten years of weather exposure, — a soft pencil
blackened area was removed from an Italian replica statue head
made of white Carrara marble.
In 2006, the same group extended the identification of the
different previous metal plates placed on the roof of a building at
about 60 m from the lidar system, by studying the spectra with
several algorithms [56]. In a first analysis, the points containing
copper were singled out by taking the maximum value of intensity
in the spectral range where copper had a large peak and dividing
by the average value on the whole spectrum. Results obtained in
this way showed a difficult discrimination between copper and
brass. In a second analysis, a linear correlation coefficient was
calculated between each spectrum in the sample set and the
copper reference spectrum. The largest values were obtained for
758 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768

Table 3
Analytical figures of merit obtained in the stand-off LIBS studies
References Particular Distance Matrix Analyte element Internal Concentration RSD Accuracy LOD SNR
conditions standard range (%) or (%) (%) (ppm a)
ratio
[3] 2.41 m Steel Mn 0.047 to 1.38
[35] 1200 °C 12 m Cr (540.9 nm)
Fe (561.5 nm)
Ni (547.6 nm)
Mo (550.6 nm)
[37] High temperature 4 m Cr (434.5 nm) Fe (440.5 nm) 0.51 to 15.71
1 mbar Ar or N2 Mn (323.1 nm) Fe (322.2 nm) 0.02 to 1.52
Ni (341.5 nm) Fe (340.8 nm) 0.08 to 3.56
0.22 mbar Ar 2.5 m Fe (430.8, 432.6,
437.6, 440.5 nm)
Cr (434.5,
435.2 nm)
[38] High temperature 1.5 m Cr (267.7 nm) Fe (278.8 nm) 530 b
Ar Cu (324.7 nm) Fe (322.2 nm) 540
Mn (293.3 nm) Fe (295.3 nm) 1040
Ni (231.6 nm) Fe (236.8 nm) 2070
[39] 35 to 45 m Fe
Cr 16.17 to 18.19
Ni 0.13 to 11.11
Ti 0.037 to 0.28
Mo 0.02 to 2.11
[41] 20 to 1200 °C 10 m Fe (561.6 nm) 10 34
Cr (540.9 nm) 16.15 to 18.35 7 109
Ni (547.6 nm) 0.21 to 10.29 8 39
Mo (550.6 nm) 0.02 to 2.20 11 21
[42] Sample in 10 m Fe
motion at Cr (540.9 nm) 0.13 to 11.11
24 cm min−1 Ni (547.6 nm) 0.02 to 0.3
and 40° to Ti (499.1 nm) 0.02 to 2.11
the laser Mo (550.6 nm)
[44] 12 m Si (288.1 nm) Ca (300.6 nm) 2.97 4370 b
Mg (279.5 nm) Ca (300.6 nm) 2.98 50
[45] 25 and 1000 °C 12 m At 1000 °C: c At 25 °C: At 25 °C: d
Cr (379.6 nm) Fe (399.7 nm) 15.74 to 21.75 6 4490
Ni (377.5 nm) Fe (376.3 nm) 0.13 to 15.17 21 7190
Mn (403.0 nm) Fe (399.7 nm) 0.04 to 1.88 16 3320
[60,63] Mn 0.8 to 1.5
[62,63,71] In hot-cell 3m Mo
Fe
Zr
[66] 1420 °C 7.5 m Ni 1.83 540 b
Cr 2.05 1190
[4] 795 nm–75 fs 25 m Aluminum AlO + Na
contamination
795 nm–200 ps AlO
Al (669.6,
877.3 nm) + Na
contamination + O,
N from ambient
air
795 nm–5 ns AlO
Al (669.6,
877.3 nm) + Na
contamination + O,
N from ambient air
[35] 25 °C Ablation Al (394.4 and 50
at 6 m 396.1 nm)
600 °C Collection 92
at 25, 80,
100 m
[40] 25 cm 1876
10 m 1902
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768 759

Table 3 (continued)
References Particular Distance Matrix Analyte element Internal Concentration RSD Accuracy LOD SNR
conditions standard range (%) or (%) (%) (ppm a)
ratio
[50] 9 mbar of gas 3, 5, 8, 12 m Al (394.4 nm) 84.88
mixture CO2 Mg (518.3 nm) 1.59
(95.3%), Si (390.5 nm) 8.7
N2 (2.7%), Cu (324.7 nm) 2.45
Ar (1.6%) Ni (352.4 nm) 1.46
3m Cr (357.8 nm) Between 11 e
Si (288.1 nm) 2 and 20 74
Mg (285.2 nm) 7
[55] 355 nm 60 m Al + Mg, Na
contamination
[67] 30 to 95 m Al (396.1 nm)
[68] 45 m O (777.2 nm) N (746.8 nm) 2.16 4.03
[82] 795 nm–75 fs Ablation Al (394.4,
at 180 m 396.1 nm)
Detection near
the sample
[4] 795 nm–75 fs 25 m Copper Cu (521.8 nm) 100 ng f
795 nm–200 ps Cu + O, N from
ambient air
[5] 800 nm–80 fs 90 m Cu
[55] 355 nm 60 m Cu
[56] 355 nm 60 m Cu + Na
contamination
[82] 795 nm–75 fs 37, 62, 90 m Cu
795 nm–∼ 200 ps Cu + O, N from
ambient air
[83] 248 nm–450 fs Ablation Brass Cu
at 6 m
Collection
at 4.5 m
[57] 355 nm 60 m Salt-covered Na (589 nm)
copper
Sample in Salt-covered Na (589 nm) ∼ 22% salt
motion silicone rubber
[37] High temperature 2.5 m Liquid Ni Ni (197.7 nm) 74
0.22 mbar Ar based alloy C (193.1 nm) 0.063
Addition of Ti (427.5 nm) 12.5
0.98% Ti to Cr (434.5 nm) 1.45 to 2.43
a liquid
Ni alloy
[67] 80 m Titanium Ti (625.8,
626.1 nm)+ H
(656.2 nm), N
(746.8 nm), O
(777.1, 777.4,
777.5 nm) from
ambient air
[56] 355 nm 60 m Lead Pb
[83] 248 nm–450 fs Ablation Pb
at 6 m
Collection
at 4.5 m
[56] 355 nm 60 m Stone Ca, Si, Al
Biotite stone Fe, Mg, Al, Na, K
[43] 12 m Slag samples Cr (520.4, 520.6, Mg (518.3 nm) 1.1 to 6.7 2100 b
520.8 nm)
Fe (489.1 nm) 0.6 to 1.7 1900
Dust
deposited on:
Bark Cr 4.8
Leave Cr 13.3
(continued on next page)
760 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768

Table 3 (continued)
References Particular Distance Matrix Analyte element Internal Concentration RSD Accuracy LOD SNR
conditions standard range (%) or (%) (%) (ppm a)
ratio
[43] Soil Cr 2.7
Dock rock Cr 1.4
Stone Cr 3.1
Fragment of wall Cr 5.5
[46] Vacuum 10.5 m Rocks Si (288.1 nm) 6 to 35 5.4
Al (308.2 nm) Si 0 to 6 13.3 5.2
Al (394.4/396.2 nm) Si 0 to 6 6.7 24
Mg (285.1 nm) Si 0 to 30 5.9 20.9
Ca (315.8 nm) Si 0 to 15 8 1.1
Ca (317.9 nm) Si 0 to 15 12.9 6.1
[22,70] 5 Torr CO2 19 m Synthetic Ba (455.4 nm) 5.5 21 b
silicates Cr (267.71 nm) 8.2 39
Cu (327.39 nm) 10 43
Hg (435.8 nm) 27 647
Li (670.7 nm) 8.8 20
Ni (352.4 nm) 14 224
Pb (405.7 nm) 13 95
Sn (303.4 nm) 14 84
Sr (407.7 nm) 6.3 1.9
[48] 2m Rock powder CaO SiO2 0.01 to 2.3 22
standards CaO SiO2 N 0.06 13
Basalt, dolostone, SiO2, Fe2O3, CaO,
altered rhyolites, Al2O3, MgO, TiO2
iron oxides
[49] 7 Torr CO2 Collection Certified soils Al (396.1 nm) 7 24000 g
at 5.3 m and stream Ba (455.3 nm) 20 70 e
sediments Ca (393.3 nm) 7 1100
Fe (404.5 nm) 17 30000 g
K (766.49 nm) 13 2000
Li (670.7 nm) 40 10
Mg (280.2 nm) 5 190
Mn (403.0 nm) 20 300
Na (588.9 nm) 25 440
Si (288.1 nm) 6 90000 g
Sr (407.7 nm) 30 30
Ti (398.9 nm) 33 1000
[50] 9 mbar of gas 3, 5, 8, 12 m Basalt Al (394.4 nm) 5.58
mixture CO2 Mg (518.3 nm) 9.16
(95.3%), Si (390.5 nm) 28
N2 (2.7%), Na (589.6 nm) 1.61
Ar (1.6%) Ca (393.3 nm) 2.66
Fe (438.3 nm) 6.01
3m Pure sulfur, Pyrite, S (416.2 nm) 13 to 100
Galena, Covellite
NaCl, KCl Cl
[51] 7 Torr CO2 Collection Dar al Gani SiO2 (288.1 nm) 49.63 5.8 4.6
at 5.4 m Martian meteorite FeO 15.16 13.4 8.6
CaO 6.31 20.4 11.2
MgO 18.74 13.9 5.5
TiO2 (335.4 nm) 0.66 40.9 79.4
Al2O3 5.03 18.1 17.5
Na2O (589.5 nm) 0.66 48.5 19.8
Zagami SiO2 (288.1 nm) 52.92 6.8 4.0
Martian FeO 17.11 15.2 4.3
meteorite CaO 9.91 15.0 4.6
MgO 10.83 10.1 3.6
TiO2 (335.4 nm) 1.02 46.1 28.5
Al2O3 5.56 17.4 6.8
Na2O (589.5 nm) 0.68 51.5 24.1
Andesite pressed SiO2 (288.1 nm) 54.82 5.1 2.5
powder standard Fe2O3 6.22 39.4 1.2
CaO 6.69 7.3 3.3
MgO 7.86 4.1 2.4
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768 761

Table 3 (continued )
References Particular Distance Matrix Analyte element Internal Concentration RSD Accuracy LOD SNR
conditions standard range (%) or (%) (%) (ppm a)
ration
[51] TiO2 (335.4 nm) 0.73 8.2 8.3
Al2O3 14.62 4.9 4.6
Na2O (589.5 nm) 4.61 23.2 39.7
[52] 532 nm 8.3 m Gypsum Ca, Na, H
Anhydrite Mg, Ca, Na, Sr, Li
Barite Ba, Sr
Diopside Si, Mg, Ca, Na, H
Dolomite Mg, Ca, Na
Chalk Mg, Ca, Na, Sr
[53] 10 m Dolomite Ca (534.9 nm) Mg (517.3 nm) 1/1 mol.%
Pink coral Ca (534.9 nm) Mg (517.3 nm) 89.3/10.7 0.5
mol.%
[58] 9 mbar CO2 3m Basalt O (777.1 nm) 45.8 1 to 4
Si (386.1 nm) 22.4 1 to 26
Fe (404.4 nm) 9.16 11 to 44
Al (736.1 nm) 8.47 0 to 37
Ca (443.3 nm) 6.2 1 to 30
Mg (383.0 nm) 3.71 14 to 99
Na (588.7 nm) 2.56 6 to 49
Ti (498.0 nm) 1.43 2 to 15
K (766.2 nm) 0.79 13 to 91
Sr (407.5 nm) 0.035 2 to 97
Ba (493.2 nm) 0.038 14 to 93
Limestone O (777.1 nm) 46.7 4 to 32
Si (386.1 nm) 0.56 13 to 1052
Fe (404.4 nm) 0.05 797 to 5688
Al (736.1 nm) 0.17 1645 to 12219
Ca (443.3 nm) 37.9 1 to 104
Mg (383.0 nm) 0.27 13 to 95
Na (588.7 nm) 0.074 0 to 118
Ti (498.0 nm) 0.001 79 to 5304
K (766.2 nm)
Sr (407.5 nm) 0.014 0 to 100
Ba (493.2 nm) 0.001 99 to 2123
Gabbro O (777.1 nm) 45.0 0.4 to 2
Si (386.1 nm) 22.3 3 to 37
Fe (404.4 nm) 8.6 1 to 21
Al (736.1 nm) 8.41 0 to 37
Ca (443.3 nm) 6.11 2 to 24
Mg (383.0 nm) 3.92 19 to 99
Na (588.7 nm) 2.56 0 to 49
Ti (498.0 nm) 1.38 21 to 58
K (766.2 nm) 0.95 2 to 64
Sr (407.5 nm) 0.033 2 to 99
Ba (493.2 nm) 0.029 20 to 96
Trachy-andesite O (777.1 nm) 48.2 5 to 8
Si (386.1 nm) 25.7 0.2 to 23
Fe (404.4 nm) 6.41 2 to 143
Al (736.1 nm) 7.83 1 to 9
Ca (443.3 nm) 0.58 98 to 202
Mg (383.0 nm) 3.95 11 to 99
Na (588.7 nm) 3.34 8 to 31
Ti (498.0 nm) 1.02 13 to 31
K (766.2 nm) 2.57 6 to 50
Sr (407.5 nm) 0.010 20 to 93
Ba (493.2 nm) 0.044 10 to 92
Obsidian O (777.1 nm) 48.0 10 to 11
Si (386.1 nm) 33.7 11 to 21
Fe (404.4 nm) 1.31 42 to 90
Al (736.1 nm) 7.29 1 to 93
Ca (443.3 nm) 0.94 6 to 91
Mg (383.0 nm) 0.21 8 to 95
(continued on next page)
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Table 3 (continued)
References Particular Distance Matrix Analyte element Internal Concentration RSD Accuracy LOD SNR
conditions standard range (%) or (%) (%) (ppm a)
ratio
[58] Na (588.7 nm) 3.13 15 to 45
Ti (498.0 nm) 0.15 27 to 84
K (766.2 nm) 4.02 22 to 38
Sr (407.5 nm) 0.010 18 to 89
Ba (493.2 nm) 0.080 8 to 89
Trachyte O (777.1 nm) 48.1 11
Si (386.1 nm) 30.3 5 to 11
Fe (404.4 nm) 2.82 7 to 231
Al (736.1 nm) 7.99 4
Ca (443.3 nm) 0.86 81 to 83
Mg (383.0 nm) 0.41 0 to 96
Na (588.7 nm) 3.45 4 to 21
Ti (498.0 nm) 0.32 11 to 12
K (766.2 nm) 4.86 15 to 29
Sr (407.5 nm) 0.029 0 to 98
Ba (493.2 nm) 0.10 3 to 97
[47] 7 Torr CO2 4m Water ice/10% Ba (455.4 nm) 12 b
soil mixtures Li (670.8 nm) 6
Mn 15
Sr (460.7 nm) 1
Ti 111
6.5 m Ba (455.4 nm) 66
Li (670.8 nm) 3
Mn 101
Sr (460.7 nm) 2
Ti 520
[34] 1m Mineral melt Si, Al, Mn, 1000 or
Fe, Mg, Ca better h
[54] 3m 1000 ppm Tc 25 d
technetium
in water
[68] 45 m DNT solution O (777.2 nm) N (746.8 nm) 2.9 8.36
deposited on the
same Al foil
30 m Acetone H (656.2 nm) C2 (510 nm) 4.29
O (777.2 nm) H (656.2 nm) 0.82
O (777.2 nm) K (766.5 nm) 1.42
O (777.2 nm) N (746.8 nm) 4.23
Na (589 nm) C2 (510 nm) 2.19
Human H (656.2 nm) C2 (510 nm) 1.15
fingerprint O (777.2 nm) H (656.2 nm) 1.26
O (777.2 nm) K (766.5 nm) 0.49
O (777.2 nm) N (746.8 nm) 6.14
Na (589 nm) C2 (510 nm) 4.10
TNT solution H (656.2 nm) C2 (510 nm) 3.50
O (777.2 nm) H (656.2 nm) 0.73
O (777.2 nm) K (766.5 nm) 1.14
O (777.2 nm) N (746.8 nm) 4.49
Na (589 nm) C2 (510 nm) 2.41
TNT fingerprint H (656.2 nm) C2 (510 nm) 1.71
O (777.2 nm) H (656.2 nm) 1.08
O (777.2 nm) K (766.5 nm) 1.31
O (777.2 nm) N (746.8 nm) 7.02
Na (589 nm) C2 (510 nm) 1.19
a
ppm means parts per million (μg/g).
b
Here, LOD = 3 s/m where s is the standard deviation of the analyte signal determined from the sample of lowest analyte concentration, and m is the linear slope of
the calibration curve.
c
The concentration at 1000 °C is determined from the calibration transfer method at 25 °C.
d
Here, LOD is defined from the spectrum background equivalent concentration.
e
Here, LOD is determined as recommended in ISO 11843-2 [84].
f
Here, LOD is determined from the SNR of 110 on the spectrum.
g
Limits of quantification are determined for Si, Al, Fe as recommended in ISO 11843-2 [84].
h
Here, LOD is estimated from the XRF reference analysis.
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
the copper points but also quite high values were observed for
the brass points. Finally, a Principal Component Analysis (PCA)
allowed distinguishing five groups corresponding to the five
different materials with copper and brass quite close to each
other and iron close to stainless steel. Remote LIBS measure-
ments on a few different stones and minerals were also tried to
show interest for mining applications, where the results can
guide the mining operations to the areas of highest mineral con-
tent. LIBS spectra from a stone containing a mixture of calcite
(CaCO3) and quartz (SiO2) with some contamination of clay
with Al evidenced Ca, Si, Al lines while LIBS spectra from a
biotite stone (K(Mg,Fe)3AlSi3O10(OH)2) showed Fe, Mg, Al,
Na and K peaks. Remote ablative cleaning was performed on an
Italian garden statue by scanning the laser beam on the target
located 60 m away from the system but the LIBS signal to noise
ratio was not enough to control the cleaning process spectro-
scopically. The authors predicted a range capability of at least
300 m for the system equipped with a modified telescope mirror
(use of a parabolic mirror with strongly reduced aberration
which would conduct to reduced focused spot size and to the use
of the full laser power without running the risk of damage of the
folding mirror). However, the authors indicate that for cultural
heritage applications, a range of 100 m would suffice and would
also allow for convenient target inspection.
3.2.7. Stand-off analysis of liquid samples
Although stand-off LIBS analysis was usually used on solid
samples, only one study [54] described the analysis of liquid
samples with a telescopic arrangement of focal length adjustable
in the range 2 to 5 m. The plasma light was collected both off-axis
(10° from the laser axis) and on-axis using a novel method to
separate the laser beam from the plasma light based on the
principle of frustrated total internal reflection. Several approaches
of liquid sampling were tested (— free surface, — aluminum plate
with central hole of 3 to 4 mm diameter placed on the surface to
have access to a well-confined volume of liquid with an optional
enclosure to pressurize the interaction spot, and — laminar water
jet) and the final solution adopted for the majority of experiments
was the use of a laminar water jet. The remote telescopic system
was used to detect in aqueous solution, technetium, possible
element encountered in solvent flows during reprocessing of
nuclear fuels. Spectra of 1000 ppm technetium in water placed in
a Petry dish at a distance of 3 m from the laser system operating at
a repetition rate less than 1 Hz to minimize splashing of the
solution were recorded for different delay times. From these
recorded spectra, it was estimated that Tc levels down to about
25 mg/l could be detected with the employed remote LIBS system.
4. Stand-off LIBS analysis with femtosecond pulses
4.1. Remote analysis by conventional LIBS using femtosecond
laser pulses
Except for a few research papers in the analytical literature,
most LIBS applications are based on nanosecond pulsed lasers
because they are cheaper and more reliable than picosecond and
femtosecond lasers. As shown in the previous section, stand-off
763
LIBS measurements performed with nanosecond pulses have
been reported at distances of tens of meters and to further
increase the operation distance, there has been interest in recent
years in evaluating picosecond and femtosecond lasers for
remote LIBS applications.
In 2004, remote analysis was demonstrated by using
conventional LIBS on copper and aluminum samples located
25 m away from a terawatt femtosecond laser (795 nm, 10 Hz,
75 fs, up to 350 mJ) [4]. The ability of the same laser system to
generate pulses in the picosecond (200 ps) and nanosecond
(5 ns) regimes allowed direct comparison of results obtained
with the three pulse durations. The beam was expanded and
focused at a distance of 25 m by an ×3 beam expander
composed with a convex and a concave mirror. A Newtonian
telescope ( f/5, 10 cm primary mirror diameter) located beside
the laser collected the plasma light at a position adjacent to but
not collinear with the path of the incident pulses. The plasma
light collected at the focus of the telescope was coupled into a
bundle of fiber optics with a circular section for the input end
and a rectangular section for the output end which was adapted
to the entrance slit of a Czerny-Turner spectrometer ( f/8,
f = 500 mm, 600 lines/mm grating) equipped with an ICCD
camera detector. Femtosecond pulses were found to produce
LIBS spectra free of emissions from elements in the ambient
gas, and this was not the case for LIBS spectra created either by
the picosecond or nanosecond pulses. This is an appreciable
advantage for quick and precise identification of elements in an
unknown and complex sample. The high signal to noise ratios
induced by femtosecond pulses would allow measuring Cu with
an absolute detection limit of 100 ng at a distance of 25 m.
Emissions from plasmas produced by femtosecond and
picosecond pulses were observed to decay with a time constant
of several microseconds, comparable with that observed for
plasma induced by nanosecond pulses, allowing the application
of standard gated detectors. The minimum laser pulse duration,
e.g. the maximum power density on the target was found not to
produce the strongest LIBS emission signal and a more efficient
detection was obtained with pulse duration optimization for
each type of studied material.
4.2. Remote analysis by filament-induced breakdown
spectroscopy
A new approach based on the use of atmospheric filamentation
formed by ultra-short and ultra-intense laser pulses propagating in
air has been tested for long distance LIBS experiments. Filaments
appear in non-linear propagation of ultra-short laser pulses, as a
result of a dynamic equilibrium between Kerr self-focusing and
defocusing caused by the plasma generated in the air. Indeed,
when a laser pulse with peak power larger than a critical power
(several GW in air) propagates through air or other medium
transparent at the laser wavelength, it undergoes self-focusing due
to the non-linear part of the refractive index of the medium (the
optic path at the center of the beam is longer than in the edges
creating a lens acting to focus the laser pulse). This focusing
results in ionization of the medium and formation of plasma that
acts to defocus the beam. Once self-focused laser intensity
764 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
becomes high enough, a dynamic equilibrium establishes
between the two processes resulting in self-guided channels
called filaments. In these filaments whose length has been
observed to be 200 m and diameter of about 100 μm, the intensity
reaches 1013–1014 W/cm2 [80] and leads to ablation on a target.
The subsequent plasma line emission can then be detected by a
suitable detection system coupled to a telescope remotely
collecting the plasma light.
Femtosecond laser systems generating powers on the order
of 1014 W that are needed for filamentation are currently
laboratory instruments because of their complexity, size and
requirement for a controlled operating environment. For the first
time in 2002, Wille et al. [81] described the Teramobile system,
which resulted from the joint collaboration between French and
German institutions to develop a new mobile femtosecond
multi-terawatt laser and detection system that could be
transported to different field sites. The system was based on a
chirped pulse amplification laser (793 nm central wavelength,
16 nm bandwidth) embedded in a standard freight container
with a detection system, mainly designed to perform Lidar
measurements, as well as a mobile detection unit allowing a
characterization of the non-linear propagation of high-power
pulses over long distances. The detection system inside the
container consisted of a vertically mounted telescope and two
detection channels. The first channel consisted of a spectro-
graph for spectrally and temporally resolved measurements, the
second one was used to measure depolarization for investiga-
tions of the white light generation, scattering in the filaments
and atmospheric particles characterization. The first results
obtained with this system (793 nm, 330 mJ, minimum pulse
duration of 100 fs, beam diameter of 5 cm) included formation
and length of self-guided filaments observed over 100 m
distance, Lidar measurements, and high-voltage discharge
triggering.
In 2004 using this system, it was demonstrated that the self-
guided filaments generated by high-power, ultra-short laser
pulses could deliver high laser intensities at distances up to 90 m
without focusing, allowing a remote filament-induced break-
down spectroscopy (R-FIBS) scheme [5]. The Teramobile laser
pulses (80 fs, 250 mJ at 800 nm, 10 Hz) were collimated to 3 cm
diameter and directed to tilted metal samples (copper and steel
plates) located at distances from 20 to 90 m. To begin the
filament production 7–8 m in front of the target, the pulses were
shaped with a negative chirp corresponding to pulse durations
up to 800 fs. Such arrangement led to the production of a
multiple-filamentation pattern on the target surface, exhibiting
around 30 filaments across the beam profile. The backward
emitted light from the filament-induced breakdown was
collected by a telescope (20 cm) and analyzed by a spectrometer
and ICCD camera located near the laser with an angle. LIBS
spectra obtained from the samples located 90 m away from the
laser and detection systems showed no broad-band blackbody
emission on the 100 ns time scale, demonstrating that the
filament-excited plasma was cold, providing a better contrast
than in classical LIBS. In these spectra, the typical lines of Cu(I)
and Fe(I) were clearly visible in the 500–550 nm spectral
window, showing that R-FIBS could perform remote elemental
analysis at a distance of 90 m. Under the same conditions,
uncompressed (200 ps) and unseeded (typically 5 ns) laser
pulses yielded neither ablation nor LIBS signal. Over the 20–
90 m range investigated, the measured R-FIBS signal multiplied
by a factor r2 (to compensate for the 1/r2 term due to the solid
angle collected by the telescope) was found independent of the
sample distance r. The authors further checked that by keeping a
fixed distance of 7 m between the detection system and the
sample and by moving the laser up to 90 m, the R-FIBS signal
did not depend significantly on the propagation distance of the
laser beam before the filaments hit the sample, in contrast with
remote LIBS excited by a focused beam [4]. The signal to noise
ratio decreased with the detection distance, and its extrapolated
values dropped to 1 around 150 m, the lower limit distance
which could be achieved with this non-optimized system.
Improvements in the detection system efficiency should
enhance the R-FIBS signal by an expected factor of 100,
allowing measurements at distances up to the kilometer range.
This technique could be practical for remote analysis on
hazardous or unreachable spots, such as polluted sites, nuclear
plants or chemical leakages.
In 2005, the same results were presented evidencing a quasi-
periodical grating like ripple structure on the surface of a copper
sample irradiated by filaments induced at 90 m by the high
intensity femtosecond pulses of the Teramobile system,
demonstrating ablation of the target surface by the filaments
propagating in air [82]. The R-FIBS spectra were free of
emission lines due to oxygen and nitrogen from ambient air,
similar to the spectra obtained using femtosecond pulses with
conventional LIBS [4]. To investigate the capability of
filaments to generate plasma at distances exceeding the limit
of 150 m estimated with the used detection system, an
aluminum target was positioned at a distance of 180 m from
the laser and irradiated by filaments. The Al plasma emission
lines at 394.4 and 396.1 nm were detected without temporally
gating the detection system. The decay time of plasma emission
was estimated from the photomultiplier signal to be about
130 ns which was much shorter than lifetimes observed for
plasmas induced by femtosecond, picosecond and nanosecond
pulses in conventional LIBS at shorter distances [4]. Finally, a
parameter estimation based on the experimental data at 90 m
showed that kilometer-range R-FIBS operation would be
possible.
The first experimental demonstration of remote LIBS using
sub-picosecond UV laser filaments created in the atmosphere
was reported by Tzortzakis et al. in 2006 [83] for the analysis of
objects of cultural heritage. An excimer KrF laser generating
450 fs pulses at 248 m was spatially filtered and focused in air
with a 10 m focal length lens to produce at about 5 m from the
lens, UV filaments which propagated over more than 5 m. The
local intensity of the filamented beam was high enough to
generate a plasma on the surface of different solid targets placed
along the path of the filaments. The plasma light was collected
remotely with a Cassegrain telescope (80 mm aperture, f/6.3)
placed close to the laser but slightly off axis, and directed
through a fiber optic to a spectrograph equipped with an ICCD
detector. For comparison, the authors used a standard setup
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
where an optical fiber connected to the same detection system
was placed near the plasma. Comparison of LIBS spectra
recorded locally and remotely for brass and lead (two elements
extensively used in cultural heritage monuments and sculptures)
placed 6 m away from the lens, with the collecting telescope at
4.5 m from the target, showed that LIBS was able to clearly
identify these two elements with smaller lines signals in the
remote mode. This was a consequence of the significantly
narrower telescope collection solid angle than that of the optical
fiber in local measurement. Filament induced LIBS spectra
recorded locally for different stones used in historic monuments
(cement, limestone, red clay, white marble) had quite similar
emission features due to the fact that all these samples had close
compositions, making stone recognition difficult. Two spectra
recorded locally for lead at two different positions on the path of
the UV filaments (6.8 and 6.0 m) had an identical structure
(same relative emission line intensity) but differed in the total
amplitude because in all produced filaments, the intensity should
be fixed but the number of filaments and their distribution in
space should change. This intensity self-regulation in the laser
filaments provides the ideal conditions for applying remote UV
femtosecond filaments in a scanning mode allowing the rapid
mapping of sculpture and large monuments.
5. Synthesis of stand-off LIBS performance
Finally, we synthesize the performance of stand-off LIBS
experimental results found in literature for different matrices.
The main analytical figures of merit used to characterize the
capabilities of an analysis method are limit of detection (LOD),
precision (RSD), and accuracy. They are presented in Table 3
with the concentration range or ratio investigated and, for some
elements the signal to noise ratio (SNR). The results must be
considered in view of the experimental parameters used in each
reference (laser pulse energy and duration, analysis and col-
lection distance, atmosphere, spectra acquisition parameters…).
When no indication on the experimental conditions is given in
this table, it means that the experiments were performed in air at
atmospheric pressure and ambient temperature, with the
1064 nm laser wavelength and a pulse duration of a few ns.
Exceptions to these conditions are specified in the table.
Concerning the metal targets, the principal elements studied in
steel samples placed until 45 m from the LIBS instrument were Fe,
Cr, Ni, Mn and Mo present at relatively high concentration in these
samples (between 0.02 and several tens of percent). The limits of
detection determined for analysis distances between 1.5 and 12 m
were generally higher than 500 ppm with RSD values on LIBS
signal lower than 10%. The studies led on aluminum samples for
analysis distances until around 100 m principally concerned the
detection of the Al lines. Only one study realized at 3 m reported
limits of detection of a few tens of ppm for Cr, Si and Mg in
aluminum, with RSD values between 2 and 20%. Copper or brass
samples have also largely been investigated, principally with
stand-off LIBS systems equipped with sub-nanosecond laser
pulses and Cu detection has been demonstrated until 90 m. Other
metals like nickel, titanium and lead have also been used to show
the feasibility of detecting the major elements at stand-off
765
distance. The studies realized on geological samples have
principally been performed in reduced pressure of CO2 to simulate
analyses in a Martian atmosphere and demonstrate the feasibility
of the stand-off LIBS technique for planetary exploration. They
principally concerned detection of major elements (Si, Ca, Fe, Al,
Mg, Ti, Na, K, Mn) but also some minor or trace elements like Sr,
Ba, Li, Cr contained in environmental samples placed at analysis
distances shorter than 20 m. The detection limits were found of a
few hundreds of ppm and below with RSD values generally lower
than 15%. The accuracy of the quantitative results depended on
the calculation method (calibration curve, internal standardization,
calibration-free method), on the matrix and on the studied element,
and could reach values below 5%. The stand-off analysis of a
liquid sample allowed determination of a detection limit of 25 ppm
Tc in water placed at 3 m distance. It has to be notified that the
analytical results depend on the considered elemental lines and
their choice varies from one paper to another. The RSD is not
determined from the same number of LIBS measurements in all
the studies. We also note that several methods have been
employed for detection limit calculation. Thus, a precise
comparison of the different results is very difficult due to the
various experimental conditions used in the different studies (laser
irradiance, laser focusing and plasma light collection distances,
environmental conditions, signal acquisition parameters…).
6. Conclusion
This review presents stand-off LIBS analysis results in an
open-path configuration where the laser beam and the plasma
light are transmitted through the atmosphere. Stand-off LIBS
analysis has been tested in a large field of applications
(metallurgical and nuclear industry, environmental control,
planetary exploration, cultural heritage…) but only a limited
number of research groups is studying each application. Stand-
off LIBS has mainly been used with nanosecond pulses for
analysis of solid and liquid samples located up to tens of meters
from the instrument. Analysis of solid samples has also been
demonstrated at a distance of 25 m using conventional LIBS
with femtosecond pulses. To extend LIBS analysis to very long
distances with kilometer range predicted, a new approach based
on filaments induced in the atmosphere by the high-power
densities of femtosecond pulses has been employed.
A large number of optical configurations based on refracting
or reflecting telescopes have been utilized to tightly focus the
laser beam at long distances and reach the power density
required for plasma formation, and to collect sufficient plasma
light. In ideal case, by supposing no plasma characteristics
changes with the working distance increase, the LIBS signal
must be proportional to the solid angle of collection and must
decay with the inverse square analysis distance. In real case, the
focusing capabilities of the optical systems degrade with the
analysis distance leading to a decrease of the laser irradiance at
the target surface and to changes in the plasma characteristics
(temperature, density). Thus, when the analysis distance grows,
the elemental line ratios can evolve, the LIBS spectra can
lose information on the elements present at low concentration
in the samples or on the least sensitive emission lines. As a
766 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
consequence, at very long distances, the lonely detected
elements will be the major components of the matrices and it
will be only possible to perform a qualitative analysis. Quan-
titative analysis can be envisaged on a limited range of working
distance where LIBS signal can be recorded for the minor and
trace constituents of the samples. The majority of studies
reported in the stand-off distance LIBS literature have obtained
quantitative results by applying the usual method of the
calibration curves through reference materials. A local calibra-
tion can be transferred to a distance using a transfer function
which takes into account the changes in instrumental factors and
in plasma conditions with the analysis distance variation. This
transfer function can be obtained by comparing the elemental
signal of a known concentration sample placed under defined
conditions with the local calibration curve. This method can be
valuable provided the analysis distance is constant as is the case
in many industrial environments. However, it is foreseeable that
this standard approach is not well-adapted to real field
measurements unless determining a transfer function for any
distance. But especially in field analyses, the samples have an a
priori unknown composition and the calibration method cannot
be applied. Therefore, the physical processes originating the
spectra must be characterized and modeled with the purpose of
developing calibration-less procedures leading to quantitative
analysis at stand-off distance. Calibration-less algorithms have
already been patented by Palleschi et al. (Calibration-Free LIBS
method [76]) and tested in one paper of Sallé et al. [58] for Mars
surface analysis at tens of meters but research efforts remain to
be made from both the theoretical and experimental sides of the
problem. In general, this challenge is very important for the
LIBS technique, particularly well-suited for applications such as
field analyses where no reference samples are available and
other analytical techniques do not give satisfactory results.
Acknowledgments
Beatrice Salle wishes to thank Annemie Bogaerts for asking
her to write this review paper. She would also like to acknowledge
the CNES, the French national institute for space research,
which supported her work about LIBS for stand-off analysis
of Mars.
References
[1] J. Debras-Guédon, N. Liodec, De l'utilisation du faisceau issu d'un
amplificateur à ondes lumineuses par émission induite de rayonnement
(laser à rubis), comme source énergétique pour l'excitation des spectres
d'émission des éléments, C.R. Acad. Sci., Paris 257 (1963) 3336–3339.
[2] U. Panne, Laser remote sensing, Trans. Anal. Chem. 17 (1998) 491–500.
[3] D.A. Cremers, The analysis of metals at a distance using laser-induced
breakdown spectroscopy, Appl. Spectrosc. 41 (1987) 572–578.
[4] Ph. Rohwetter, J. Yu, G. Méjean, K. Stelmaszczyk, E. Salmon, J.
Kasparian, J.-P. Wolf, L. Wöste, Remote LIBS with ultrashort pulses:
characteristics in picosecond and femtosecond regimes, J. Anal. At.
Spectrom. 19 (2004) 437–444.
[5] K. Stelmaszczyk, Ph. Rohwetter, G. Méjean, J. Yu, E. Salmon, J.
Kasparian, R. Ackermann, J.-P. Wolf, L. Wöste, Long-distance remote
laser-induced breakdown spectroscopy using filamentation in air, Appl.
Phys. Lett. 85 (2004) 3977–3979.
[6] W.T. Chan, R.E. Russo, Study of laser-material interactions using
inductively coupled plasma-atomic emission spectrometry, Spectrochim.
Acta Part B 46 (1991) 1471–1486.
[7] E. Tognoni, V. Palleschi, M. Corsi, G. Cristoforetti, N. Omenetto, I.
Gornushkin, B.W. Smith, J.D. Winefordner, From sample to signal in laser-
induced breakdown spectroscopy: a complex route to quantitative analysis, in:
A. Miziolek, V. Palleschi, I. Schechter (Eds.), Laser Induced Breakdown
Spectroscopy (LIBS): Fundamentals and Applications, Cambridge University
Press, 2006, Chapter 3.
[8] R.A. Multari, L.E. Foster, D.A. Cremers, M.J. Ferris, Effect of sampling
geometry on elemental emissions in Laser-Induced Breakdown Spectros-
copy, Appl. Spectrosc. 50 (1996) 1483–1499.
[9] R.A. Al-Wazzan, J.M. Hendron, T. Morrow, Spatially and temporally
resolved emission intensities and number densities in low temperature
laser-induced plasmas in vacuum and in ambient gases, Appl. Surf. Sci.
96–98 (1996) 170–174.
[10] J.M. Vadillo, M. Milan, J.J. Laserna, Space and time-resolved laser-
induced breakdown spectroscopy using charge-coupled device detection,
Fresenius' J. Anal. Chem. 355 (1996) 10–15.
[11] D.A. Rusak, M. Clara, E.E. Austin, K. Visser, R. Niessner, B.W. Smith, J.D.
Winefordner, Investigation of the effect of target water content on a laser-
induced plasma, Appl. Spectrosc. 51 (1997) 1628–1630.
[12] B.C. Castle, K. Visser, B.W. Smith, J.D. Winefordner, Spatial and temporal
dependence of lead emission in Laser-Induced Breakdown Spectroscopy,
Appl. Spectrosc. 51 (1997) 1017–1024.
[13] R.K. Thareja, A. Misra, S.R. Franklin, Investigation of laser ablated metal
and polymer plasmas in ambient gas using fast photography, Spectrochim.
Acta Part B 53 (1998) 1919–1930.
[14] I. Schechter, V. Bulatov, Plasma morphology, in: A. Miziolek, V. Palleschi, I.
Schechter (Eds.), Laser Induced Breakdown Spectroscopy: Fundamentals
and Applications, Cambridge University Press, 2006, pp. 40–121, Chapter 2.
[15] H.R. Griem, Plasma Spectroscopy, McGraw-Hill, New York, 1964.
[16] W. Lochte-Holtgreven, Plasma Diagnostics, North Holland Publishing,
Amsterdam, 1968.
[17] G.J. Bastiaans, R.A. Mangold, The calculation of electron density and
temperature in Ar spectroscopic plasmas from continuum and line spectra,
Spectrochim. Acta Part B 40 (1985) 885–892.
[18] N. André, C. Geertsen, J.L. Lacour, P. Mauchien, S. Sjostrom, UV laser
ablation optical emission spectrometry on aluminum alloys in air at
atmospheric pressure, Spectrochim. Acta Part B 49 (1994) 1363–1372.
[19] M. Milan, J.M. Vadillo, J.L. Laserna, Removal of air interference in Laser-
Induced Breakdown Spectrometry monitored by spatially and temporally
resolved charge-coupled device measurements, JAAS 12 (1997) 441–444.
[20] D.A. Cremers, L.J. Radziemski, History and fundamentals of LIBS, in: A.
Miziolek, V. Palleschi, I. Schechter (Eds.), Laser Induced Breakdown
Spectroscopy: Fundamentals and Applications, Cambridge University
Press, 2006, pp. 8–9, Chapter 1.
[21] D.A. Cremers, L.J. Radziemski, Handbook of Laser-Induced Breakdown
Spectroscopy, John Wiley, 2006, pp. 5–7.
[22] A.K. Knight, N.L. Scherbarth, D.A. Cremers, M.J. Ferris, Characterization
of laser-induced breakdown spectroscopy (LIBS) for application to space
exploration, Appl. Spectrosc. 54 (2000) 331–340.
[23] Y. Iida, H. Morikawa, A. Tsuge, Y. Uwamino, T. Ishizuka, Laser induced
plasmas observed with an optical imaging spectrometer, Anal. Sci. 7
(1991) 61–64.
[24] Y.I. Lee, T.L. Thiem, G.H. Kim, Y.Y. Teng, J. Sneddon, Interaction of an
excimer laser beam with metals. Part III: the effect of a controlled atmosphere
in laser-ablated plasma emission, Appl. Spectrosc. 46 (1992) 1597–1604.
[25] Y.I. Lee, K. Song, H.K. Cha, J.M. Lee, M.C. Park, G.H. Lee, J. Sneddon,
Influence of the atmosphere and irradiation wavelength on copper plasma
emission induced by excimer and Q-switched Nd:YAG laser ablation,
Appl. Spectrosc. 51 (1997) 959–964.
[26] H. Kurniawan, W. Setia Budi, A.M. Marpaung, K. Kagawa, Characteris-
tics of a laser plasma induced by irradiation of a normal-oscillation YAG
laser at low pressures, J. Phys., D, Appl. Phys. 30 (1997) 3335–3345.
[27] H. Kurniawan, Y. Ishikawa, S. Nakajima, K. Kagawa, Characteristics of
the secondary plasma induced by focusing a 10-mJ XeCl laser pulse at low
pressures, Appl. Spectrosc. 51 (1997) 1769–1780.
 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
[28] R. Brennetot, J.L. Lacour, E. Vors, A. Rivoallan, D. Vailhen, S. Maurice,
Mars analysis by laser-induced breakdown spectroscopy (MALIS):
influence of Mars atmosphere on plasma emission and study of factors
influencing plasma emission with the use of Doehlert designs, Appl.
Spectrosc. 57 (2003) 744–752.
[29] B. Sallé, D.A. Cremers, S. Maurice, R.C. Wiens, Laser-Induced
Breakdown Spectroscopy for space exploration applications: Influence
of the ambient pressure on the calibration curves prepared from soil and
clay samples, Spectrochim. Acta Part B 60 (2005) 479–490.
[30] S. Maurice, R.C. Wiens, G. Manhès, D.A. Cremers, B.L. Barraclough, J.
Bernardin, M. Bouyé, A. Cros, B. Dubois, E. Durand, S. Hahn, D. Kouach,
J.L. Lacour, D. Landis, T. Moore, L. Parès, J. Platzer, M. Saccoccio, B.
Sallé, R. Whitaker, ChemCam instrument for the Mars Science Laboratory
(MSL) rover, Lunar Planet. Sci. Conf. XXXVI, The Lunar and Planetary
Institute, Houston TX, 2005, abstr. 1735.
[31] http://marsprogram.jpl.nasa.gov/msl/mission/sc_instru_chemcam.html.
[32] http://mars.jpl.nasa.gov/msl/.
[33] P. Weibring, H. Edner, S. Svanberg, Versatile mobile lidar system for
environmental monitoring, Appl. Opt. 42 (2003) 3583–3594.
[34] U. Panne, R.E. Neuhauser, C. Haisch, H. Fink, R. Niessner, Remote
analysis of a mineral melt by Laser-Induced Plasma Spectroscopy, Appl.
Spectrosc. 56 (2002) 375–380.
[35] J.M. Vadillo, P.L. Garcia, S. Palanco, D. Romero, J.M. Baena, J.J. Laserna,
Remote, real-time, on-line monitoring of high-temperature samples by
non-invasive open-path laser plasma spectrometry, Anal. Bioanal. Chem.
375 (2003) 1144–1147.
[36] N. Ramaseder, J. Heitz, J. Gruber, D. Bäuerle, Device for the chemical
analysis of material samples and metallurgical vessel therefor, United
States Patent US 7,006,216 B2, 2006.
[37] J. Gruber, J. Heitz, N. Arnold, D. Bäuerle, N. Ramaseder, W. Meyer, J.
Hochörtler, F. Koch, In situ analysis of metal melts in metallurgical
vacuum devices by laser-induced breakdown spectroscopy, Appl.
Spectrosc. 58 (2004) 457–462.
[38] J. Gruber, J. Heitz, H. Strasser, D. Bäuerle, N. Ramaseder, Rapid in-situ
analysis of liquid steel by laser-induced breakdown spectroscopy,
Spectrochim. Acta Part B 56 (2001) 685–693.
[39] S. Palanco, J.M. Baena, J.J. Laserna, Open-path laser-induced plasma
spectrometry for remote analytical measurements on solid surfaces,
Spectrochim. Acta Part B 57 (2002) 591–599.
[40] S. Palanco, J.J. Laserna, Remote sensing instrument for solid samples
based on open-path atomic emission spectrometry, Rev. Sci. Instrum. 75
(2004) 2068–2074.
[41] P.L. Garcia, J.M. Vadillo, J.J. Laserna, Real-time monitoring of high-
temperature corrosion in stainless steels by open-path laser-induced plasma
spectrometry, Appl. Spectrosc. 58 (2004) 1347–1352.
[42] C. López-Moreno, S. Palanco, J.J. Laserna, Stand-off analysis of moving
targets using laser-induced breakdown spectroscopy, J. Anal. At. Spectrom.
22 (2007) 84–87.
[43] C. López-Moreno, S. Palanco, J.J. Laserna, Remote laser-induced plasma
spectrometry for elemental analysis of samples of environmental interest,
J. Anal. At. Spectrom. 19 (2004) 1479–1484.
[44] C. López-Moreno, S. Palanco, J.J. Laserna, Quantitative analysis of
samples at high temperature with remote laser-induced breakdown
spectrometry using a room-temperature calibration plot, Spectrochim.
Acta Part B 60 (2005) 1034–1039.
[45] C. López-Moreno, S. Palanco, J.J. Laserna, Calibration transfer method for
the quantitative analysis of high-temperature materials with stand-off laser-
induced breakdown spectroscopy, J. Anal. At. Spectrom. 20 (2005)
1275–1279.
[46] D.A. Cremers, M.J. Ferris, C.Y. Han, J.D. Blacic, D.R. Pettit, Remote
elemental analysis using laser-induced breakdown spectroscopy, SPIE Proc.
2385 (1995) 28–38.
[47] Z.A. Arp, D.A. Cremers, R.C. Wiens, D.M. Wayne, B. Sallé, S. Maurice,
Analysis of water ice and water ice/soil mixtures using Laser-Induced
Breakdown Spectroscopy: application to Mars polar exploration, Appl.
Spectrosc. 58 (2004) 897–909.
[48] R.C. Wiens, R.E. Arvidson, D.A. Cremers, M.J. Ferris, J.D. Blacic, F.P. Seelos
IV, K.S. Deal, Combined remote mineralogical and elemental identification
767
from rovers: field and laboratory tests using reflectance and laser-induced
breakdown spectroscopy, J. Geophys. Res., Planets 107 (2002) 3–1–3-14.
[49] B. Sallé, D.A. Cremers, S. Maurice, R.C. Wiens, P. Fichet, Evaluation of a
compact spectrograph for in-situ and stand-off Laser-Induced Breakdown
Spectroscopy analyses of geological samples on Mars missions, Spectro-
chim. Acta Part B 60 (2005) 805–815.
[50] B. Sallé, J.L. Lacour, E. Vors, P. Fichet, S. Maurice, D.A. Cremers, R.C.
Wiens, Laser-Induced Breakdown Spectroscopy for Mars surface analysis:
Capabilities at stand-off distances and detection of chlorine and sulphur
elements, Spectrochim. Acta Part B 59 (2004) 1413–1422.
[51] J.R. Thompson, R.C. Wiens, J.E. Barefield, D.T. Vaniman, H.E. Newsom,
S.M. Clegg, Remote Laser Induced Breakdown Spectroscopy (LIBS)
analyses of Dar al Gani 476 and Zagami Martian meteorites, J. Geophys.
Res., Planets 111 (2006).
[52] R.C. Wiens, S.K. Sharma, J. Thompson, A. Misra, P.G. Lucey, Joint
analyses by laser-induced breakdown spectroscopy (LIBS) and Raman
spectroscopy at stand-off distances, Spectrochim. Acta Part A 61 (2005)
2324–2334.
[53] H.W. Hubble, M. Ghosh, S.K. Sharma, K.A. Horton, P.G. Lucey, S.M.
Angel, R.C. Wiens, A combined remote LIBS and Raman spectroscopic
study of minerals, Lunar Planet. Sci. Conf. XXXIII, The Lunar and
Planetary Institute, Houston TX, 2002, abstr. 1935.
[54] O. Samek, D.C.S. Beddows, J. Kaiser, S.V. Kukhlevsky, M. Liska, H.H.
Telle, J. Young, Application of laser-induced breakdown spectroscopy to
in-situ analysis of liquid samples, Opt. Eng. 39 (2000) 2248–2262.
[55] R. Grönlund, M. Lundqvist, S. Svanberg, Remote imaging laser-induced
breakdown spectroscopy and remote cultural heritage ablative cleaning,
Opt. Lett. 30 (2005) 2882–2884.
[56] R. Grönlund, M. Lundqvist, S. Svanberg, Remote imaging Laser-Induced
Breakdown Spectroscopy and Laser-Induced Fluorescence Spectroscopy
using nanosecond pulses from a mobile lidar system, Appl. Spectrosc. 60
(2006) 853–859.
[57] M. Bengtsson, R. Grönlund, M. Lundqvist, A. Larsson, S. Kröll, S. Svanberg,
Remote Laser-Induced Breakdown Spectroscopy for the detection and
removal of salt on metal and polymeric surfaces, Appl. Spectrosc. 60 (2006)
1188–1191.
[58] B. Sallé, J.L. Lacour, P. Mauchien, P. Fichet, S. Maurice, G. Manhès,
Comparative study of different methodologies for quantitative rock
analysis by Laser-Induced Breakdown Spectroscopy in a simulated
Martian atmosphere, Spectrochim. Acta Part B 61 (2006) 301–313.
[59] I.M. Botheroyd, J. Young, A.I. Whitehouse, A. Duckworth, Remote
analysis of steels and other solid materials using Laser-Induced Breakdown
Spectroscopy (LIBS), CLEO/Eur. Conf. Proc., Glasgow, UK, 1998, p. 198,
abstr. CWF79.
[60] www.appliedphotonics.co.uk, Identification of cooling water tubes and
reinforcing bars within Magnox reactor pressure vessels, Application note
003.
[61] www.appliedphotonics.co.uk, LIBSCAN: Dual mode telescope/fibre-optic
probe laser spark materials characterisation instruments.
[62] www.appliedphotonics.co.uk, Remote characterisation of High-Level
Radioactive Waste at the THORP nuclear reprocessing plant, Application
note 002.
[63] A.I. Whitehouse, J. Young, C.P. Evans, Extreme LIBS, Technical digest of
Laser-Induced Plasma Spectroscopy and Applications Conference, Optical
Society of America, Orlando, Florida, 2002, abstr. WA1-1.
[64] K. Kincade, LIBS leaves the lab for field work in industry and defense,
Laser Focus World, August, 2003.
[65] A.I. Whitehouse, Laser-induced breakdown spectroscopy and its applica-
tion to the remote characterisation of hazardous materials, Spectrosc. Eur.
18 (2006) 14–21.
[66] S. Palanco, S. Conesa, J.J. Laserna, Analytical control of liquid steel in an
induction melting furnace using a remote laser induced plasma
spectrometer, J. Anal. At. Spectrom. (2004) 462–467.
[67] S. Palanco, C. Lopez-Moreno, J.J. Laserna, Design, construction and
assessment of a field-deployable laser-induced breakdown spectrometer
for remote elemental sensing, Spectrochim. Acta Part B 61 (2006) 88–95.
[68] C. López-Moreno, S. Palanco, J.J. Laserna, F. DeLucia Jr., A.W. Miziolek,
J. Rose, R.A. Walters, A.I. Whitehouse, Test of a stand-off laser-induced
768 B. Sallé et al. / Spectrochimica Acta Part B 62 (2007) 739–768
breakdown spectroscopy sensor for the detection of explosive residues on
solid surfaces, J. Anal. At. Spectrom. (2006) 55–60.
[69] www.lsa-systems.de, Transportable LIBS system for remote chemical
elemental analysis TeleLis, LSA Laser Analytical Systems and Automa-
tion GmbH, Aachen.
[70] A.K. Knight, D.A. Cremers, M.J. Ferris, N.L. Scherbarth, R.C. Wiens, J.D.
Blacic, W.M. Calvin, J.E. Nordholt, Development of a prototype
instrument for stand-off elemental analysis, Fifth International Conference
on Mars, The Lunar and Planetary Institute, Pasadena, California, USA,
1999.
[71] A.I. Whitehouse, J. Young, C.P. Evans, A. Brown, J. Franco, A. Simpson,
Remote compositional analysis of spent-fuel residues using Laser-Induced
Breakdown Spectroscopy, Waste Management 2003 Symposium, WM
Symposia, Tucson, Arizona, USA, February 2003.
[72] R. Noll, V. Sturm, M. Stepputat, A. Whitehouse, J. Young, P. Evans,
Industrial applications of LIBS, in: A. Miziolek, V. Palleschi, I. Schechter
(Eds.), Laser Induced Breakdown Spectroscopy: Fundamentals and
Applications, Cambridge University Press, 2006, pp. 427–435, Chapter
11.
[73] Applied Photonics Ltd, A.I. Whitehouse, Laser spectroscopic remote
detection of surface contamination, International Patent Application N°
PCT/GB01/00866, 2001.
[74] J.D. Blacic, D.R. Pettit, D.A. Cremers, Laser-induced breakdown
spectroscopy for remote elemental analysis of planetary surfaces, Proc.
of the International Symposium on Spectral Sensing Research, Springer
Netherlands, Maui, HI, 1992.
[75] R.C. Wiens, S. Maurice, N. Bridges, B. Clark, D.A. Cremers, K.
Herkenhoff, L. Kirkland, N. Mangold, G. Manhés, P. Mauchien, C.
McKay, H.E. Newsom, F. Poitrasson, V. Sautter, C. d'Uston, D.T.
Vaniman, S. Shipp, ChemCam science objectives for the Mars Science
Laboratory (MSL) rover, Lunar Planet. Sci. Conf. XXXVI, The Lunar and
Planetary Institute, Houston TX, 2005, abstr. 1580.
[76] V. Palleschi, A. Ciucci, S. Rastelli, E. Tognoni, Method for quantitative
analysis of atomic components of materials by LIBS spectroscopy
measurements, Patent N° WO99/49301 (1999).
[77] S.K. Sharma, S.M. Angel, M. Ghosh, H.W. Hubble, P.G. Lucey, Remote
pulsed laser Raman spectroscopy system for mineral analysis on planetary
surfaces to 66 meters, Appl. Spectrosc. 56 (2002) 699–705.
[78] http://www.esa.int/esaMI/Aurora/SEM1NVZKQAD_2.html.
[79] http://www.psrd.hawaii.edu/Oct06/libs.htlm, L.M.V. Martel, LIBS: Remote
chemical analysis.
[80] J. Kasparian, R. Sauerbrey, S.L. Chin, The critical laser intensity of self-
guided light filaments in air, Appl. Phys., B 71 (2000) 877–879.
[81] H. Wille, M. Rodriguez, J. Kasparian, D. Mondelain, J. Yu, A. Mysyrowicz,
R. Sauerbrey, J.P. Wolf, L. Wöste, Teramobile: a mobile femtosecond-
terawatt laser and detection system, Eur. Phys. J., Appl. Phys. 20 (2002)
183–190.
[82] Ph. Rohwetter, K. Stelmaszczyk, L. Wöste, R. Ackermann, G. Méjean, E.
Salmon, J. Kasparian, J. Yu, J.-P. Wolf, Filament-induced remote surface
ablation for long range laser-induced breakdown spectroscopy operation,
Spectrochim. Acta Part B 60 (2005) 1025–1033.
[83] S. Tzortzakis, D. Anglos, D. Gray, Ultraviolet laser filaments for remote
laser-induced breakdown spectroscopy (LIBS) analysis: applications in
cultural heritage monitoring, Opt. Lett. 31 (2006) 1139–1141.
[84] ISO 11843-2, Capability of detection, International Organization for
Standardization, Genève, Switzerland, 2000.