Laser-Induced Breakdown Spectroscopy-Capabilities and Limitations

Applied Spectroscopy Reviews
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Laser-Induced Breakdown
Spectroscopy—Capabilities and Limitations
David A. Cremers & Rosemarie C. Chinni
To cite this article: David A. Cremers & Rosemarie C. Chinni (2009) Laser-Induced Breakdown
Spectroscopy—Capabilities and Limitations, Applied Spectroscopy Reviews, 44:6, 457-506, DOI:
10.1080/05704920903058755
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Applied Spectroscopy Reviews, 44: 457–506, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 0570-4928 print / 1520-569X online
DOI: 10.1080/05704920903058755
Laser-Induced Breakdown
Spectroscopy—Capabilities and Limitations
David A. Cremers1 and Rosemarie C. Chinni2

1
Applied Research Associates, Inc., Albuquerque, New Mexico
2
Alvernia University, Reading, Pennsylvania
Abstract: During the past decade there has been intense activity in the field of laser-
induced breakdown spectroscopy (LIBS). This activity includes studies of laser ablation
and properties of the laser spark, the development of methods to enhance LIBS detection
capabilities, and the application of LIBS to specific analysis needs. The unique capa-
bilities of LIBS make it particularly suited for applications that cannot be addressed
by conventional analytical methods. Potential applications of the method are numerous
and several applications have been realized, resulting in on-line operating instruments.
Other applications will require that the method be developed further to improve ana-
lytical performance. Here we present an overview of the LIBS method, discussing its
many advantages and some important limitations as an analytical method and how these
relate to potential applications.
Keywords: LIBS, laser-induced breakdown spectroscopy, laser plasma, atomic

emission spectroscopy
INTRODUCTION
Over the past decade there has been intense activity in the study and devel-
opment of the analytical technique of laser-induced breakdown spectroscopy
(LIBS) for various applications. Since 2006, three books discussing various
aspects of the LIBS method have been published (1–3) and in 2008 at least 250
papers appeared in scientific journals covering topics ranging from fundamental
studies to diverse applications of the method. It is not an exaggeration to state
that LIBS is probably the most versatile method of elemental analysis that is
currently practiced. In addition, although traditionally considered an elemental
analysis method, LIBS is being developed for molecular identification. The
Address correspondence to David A. Cremers, Applied Research Associations, Inc.,

Albuquerque, NM. E-mail: dcremers@ara.com
457
458 D.A. Cremers and R.C. Chinni
range of potential applications is unequalled by any other analytical technique

and is due to its many well known advantages, which include (1) simplicity;
(2) lack of sample preparation for the analysis of gases, liquids, and solids;
(3) simultaneous multi-element detection; (4) ability to detect high and low z-
elements; (5) good sensitivity for many elements; (6) only optical access to the
target is required; (7) standoff analysis capabilities. These advantages permit
application of LIBS to real-world analysis needs that cannot be addressed by
conventional analytical methods.
It has been our experience that when one is first introduced to the LIBS
method, excitement builds over the wide range of possible applications of the
method. The ability to analyze a sample rapidly and apparently very simply
by merely pointing and firing a laser seems the stuff of science fiction that
has been realized. The Star Trek tricorder-type instrument comes to mind.
Although a truly handheld LIBS instrument has not yet been described, some
work has focused on benchmarking LIBS capabilities using miniature lasers
with plasmas generated using micro-joule energies (4). Some person-portable
instruments have been described recently in the literature (5, 6) and Figure 1
shows one fully operational instrument developed recently for short standoff
analysis.
In some cases, the high-tech image of immediate analysis using LIBS
has been realized—LIBS can provide rapid identification of materials using a
Figure 1. Person-portable “aim and interrogate” LIBS instrument for short standoff
analysis.
Laser-Induced Breakdown Spectroscopy 459
restricted library of candidate samples. A good example is the sorting of techni-

cal polymers and metals for recycling programs, where samples are segregated
according to major elements and/or element ratios. In other cases, where a
quantitative analysis is needed, the accuracy and precision provided by LIBS
may not meet analysis requirements. The quality of quantitative LIBS analysis
is subject to a number of operating parameters that may or may not be con-
trollable and this is often due to the unusual scenarios in which the technique
is deployed. Often quantitative results are compromised by the very advan-
tages of the method that make it applicable to the need from the start. One
case in point is the ability of the LIBS plasma to directly interrogate a sam-
ple without any sample preparation. For samples known to be homogeneous
the absence of sample preparation (e.g., to homogenize the sample compo-
sition) will not be an issue, but for inhomogeneous samples such as rocks,
minerals, materials with surface coatings, etc., the lack of sample preparation
complicates representative sampling. In this case, a large number of shots may
be required to average over compositional differences in a sample and the
surface composition may not be representative of the bulk material, thereby
requiring surface cleaning. Determining when a representative sampling has
occurred is problematic in these cases. As another example, for field applica-
tions, the “aim and interrogate” capabilities (Figure 1) are certainly attractive,
but changes in the analysis geometry (e.g., lens-to-sample distance) are known
to significantly change signal intensities and element ratios (7, 8), which im-
pact negatively both a concentration analysis and simple identification of the
sample. Not surprisingly, conventional analysis methods that require sample
preparation and carefully controlled analysis conditions yield higher quality
data, in general. On the other hand, when analysis conditions are more ac-
curately controlled in a LIBS measurement—eliminating the rapid point-and-
shoot analysis that is attractive for many LIBS applications—the quality of
the data increases. These considerations strongly indicate that the use of LIBS
for any application must be carefully considered in view of the conditions
under which the sample will be analyzed and the quality of the data that is
required.
The purpose of this article is to present a brief review of recent activities
in LIBS development and to critique its capabilities in light of the present state
of development.
WIDE RANGE OF APPLICATIONS OF LIBS
As noted above, due to its unique capabilities, LIBS has a wide range of
potential applications. Some of these applications have been realized in the
form of operating LIBS instruments, and many others are being investigated
for feasibility and future use. A review of past and more recently published
literature shows the diversity of potential uses of the technique and that
investigations into new uses of LIBS and fundamental studies of the laser
plasma continue unabated. The breadth of these applications and studies is
summarized in Table 1 along with corresponding references.
THE LASER PLASMA AS AN ANALYTICAL SOURCE
Detailed discussions of the laser material interaction leading to ablation and the
characteristics of the plasma formed during a LIBS measurement can be found
in the literature and in chapters of recently published books on LIBS (1–3).
Our objectives here are to discuss capabilities and limitations of the plasma as
they relate to LIBS analysis.
Uniqueness
The laser plasma is unique among excitation sources for atomic emission spec-
troscopy because it is formed by focused laser light. This lends important
capabilities to LIBS. First, the laser pulse both prepares and excites the sam-
ple in one step—a result of the very high power densities (108 –1010 W/cm2
for solids) needed to initiate the plasma. Prior to and during formation of the
plasma, some target material is ablated and vaporized to produce atoms that
are excited in the hot plasma (∼8000 K, initially). Second, the high degree of
collimation of the laser light allows the pulse to be focused to a very small
spot, providing a precisely defined analysis region important for some appli-
cations such as spatial mapping of elements (micro-analysis). This attribute
is important, for example, in the use of LIBS for analyzing objects associ-
ated with art and cultural heritage where nondestructive analysis methods are
preferred but where the micro-sampling (hence, minimally destructive) ca-
pabilities of LIBS are such that the method has been used on valuable and
sensitive art objects (9). Third, the laser pulse can be transmitted over long
distances either through open path (line-of-sight) interrogation or through a
fiber optic to form the plasma on a remotely located target providing a unique
capability for an active method of elemental analysis. Another important ca-
pability of the laser plasma is that it can be combined with other methods of
analysis and other power sources to enhance detection capabilities. The basic
LIBS method and some of the more important variants of LIBS are shown in
Figure 2.
Conventional LIBS analysis (e.g., short focusing distance) is shown in
Figure 2(a) along with collinear (b) and orthogonal (c) double-pulse analysis
methods (10, 11). In the orthogonal double-pulse arrangement the air spark
is formed above and parallel to the sample surface prior to ablation of the
sample by the second pulse. The timing between the two pulses is application
and material specific but is generally on the order of a few microseconds. In
Table 1. Some recent studies of LIBS applications and plasma characteristics
Application Topic Refs.
Coal analysis; flue gas Oxygen content in coal; delay time for coal (78–83)
measurements; LIBS machine for ash
analysis in coal; matrix effects; heavy
metals in flue gas
Cultural heritage Laser cleaning; archaeological dye analysis; (84–94)
overview of LIBS for this application;
historical parchment characterization;
painted plaster bronze age; Iron age
pottery from eastern Turkey; copper
embroidery threads on archaeological
Egyptian textiles; copper-base alloys used
in ancient artworks; microprobe for
analysis of works of art
Toxic metals in Metals in water; trace metals in water; Cr(II) (95–102)
liquids in water; Pb in water; toxic metals in
waste water; Cr in industrial wastewater;
toxic metals in wastewater from dairy
plants
Explosive, biological, Trinitrotoluene detection; IED detection; (33–36, 61, 64,
and chemical indoor biohazard detection; 65, 103–109)
detection explosive-containing residues; sensing of
explosives with UV and IR filaments;
substrate-related effects of explosives;
detection of condensed-phase explosives;
unknown powders; biological materials;
chemical and biological threat detection
Soil analysis Toxic metals in oil contaminated soil; heavy (42, 110–119)
metal contamination in soil; controlled
calibration methods; carbon in tropical
soil; soils and rock analysis;
phytoremediation of lead-contaminated
soils; ANN for Cu in soil; mobile
system-polluted soils; powder analysis
with low-pressure plasma; carbon in soil
Organics Organic analysis; nitrocompound analysis; (63, 120–127)
alcohols and proteins; glucose solution;
molecular analysis using molecular
bands; application for DNA micro-array
technology; blood and other organic
compounds
Food Trace element in fresh vegetables; food (128–130)
powders; microelements in food samples
(Continued on next page)

(Continued)
Animal tissues, Macronutrients in plants; prickly pear’s (131–135)

plants, and wood spines and glochids; characterization of
wood polychromes; heavy metal
accumulation in plant samples
Forensic Microanalysis applications; taggant (136–140)
detection; glass analysis
Minerals, oil, crystals, Trace metal detection in petroleum (141–151)
and gems; ceramics products; geologic materials; alkaline
metal crystals; determination of gem
provenance; natural calcite; granite
mapping; natural zeolitic materials; iron
clay interface; characterization of
nanocomposite oxide films; iron-ore
samples; characterization of karstic
formations
Industrial applications Automobile catalyst recycling material; (152–157)
metals, chemicals, and advanced
materials; steel industry; process control;
brick and tile industry
Medical field Simulated body fluid; biomedicine field (158–165)
applications; microleakage in dentistry;
infrastructure and veneer materials in
dentures; vitro bone-like apatite
formation; carious tooth decay; detection
of malignant skin tissue; qualitative
analysis of gallstones; ovarian cancer
detection
Lanthanide/actinide U in solids; plutonium oxide residues; Sm, (12, 166–170)
detection Eu, and Gd in aqueous solution;
radionuclide speciation; Th and U in
solution
Metals, alloys, Slag analysis in steel works; analysis of (17, 171–201)
carbon, and steel metallic alloys; analysis of gold alloys;
carbon analysis at high pressure;
standardless quantitative analysis of
alloys; metals in vacuum; brass plasma
studies; Mn determination in steel; Cu
analysis; bronze analysis; improved
detection limits for various elements in Al
alloy; quantitative Al alloy analysis; metal
sample with micro-crater LIBS; calcium
phosphate coating on Ti alloy;
self-absorbed line analysis on Al alloy;

(Continued)
depth profiling of coated super alloy; fs/ns

double-pulse LIBS for copper alloys;
matrix compositions of pure metal targets;
mass removal of Al target in air;
double-pulse with fs pulses; Pb in brass;
tin-based lead free solder; minor elements
in steel
Paints, glass, and Detection of heavy metals in paints; lead in (202–205)
cigarettes paint; single- and double-pulse on glass;
elements in cigarettes
Space Optical design for ExoMars mission; atomic (23, 24, 206,
parameter measurements; plasma 207)
parameters and laser plumes; mineral
phases and bio-signatures on Mars
Aerosol Aerosol analysis; carbonaceous aerosols; (208–214)
standoff LIBS for aerosols; modeling
aerosol analysis; alternative statistical
methods for spectral data processing;
ultrashort laser pulses in the atmosphere;
aerosolized drugs
Water and aqueous Bubble expansion properties in water; (21, 22,
solutions nanosized particles in drinking water; 215–222)
aquatic colloids; NaCl water plasma;
CaCl 2 water plasma; bulk aqueous
solutions; Pb in water; underwater plasma
Flame, pyrolysis, and Hydrocarbon-air mixtures; moveable fiber (223–228)
gas-phase analysis probe for gas-phase analysis;
measurements in methane and biodiesel
flames; nanoparticles in a pyrolysis
reactor; dielectric breakdown in gas
mixtures; hydrogen emission in methane
flow
Machining and Au film machining; microfluidic chips; (229–232)
circuits flexible printed circuit board
Polymers Analysis of etched polytetrafluoroethylene; (233–235)
polymers in plastic waster; classification
of polymers
Surfaces and films Electrode surface analysis; deposition of (236–244)
oxides; thin film deposition and fs/ns
LIBS; particular matter on substrates;
nanoscale surface analysis; analysis of
titanium oxide coating; Ge in silicon
oxides substrates; nondestructive surface
chemical analysis

(Continued)
Plasma characteristics Optical far- and near-field plasmas; ambient (245–265)

pressure studies; early plasma dynamics;
UV-induced plasma density; laser-induced
plasma expansion; magnetic effect on
plume images; ns plasmas from an Al
target; plasmas from ns bursts in the mJ
burst energy regime; plasma parameters
and self-absorption on plasmas; focusing
distance and pulse energy on plasmas;
distilled water plasma self-absorption
parameters; LTE conditions in the plasma
for Al; plasma properties of Sr; plasma
characterization on brass alloys; oxygen
plasma at room temperature; double-pulse
laser ablation and LIBS; Ca plasma
studies; plasma stoichiometry method
variants of LIBS, the plasma can be interrogated with a second laser pulse
(non-plasma forming) tuned to excite certain transitions in a species of interest
within the plasma (12) to enhance detection (d) or absorption measurements
can be carried out (13) by passing spectrally broad light or light from a hollow
Figure 2. LIBS analysis methods and demonstrated variants. The variants are dis-
cussed in the text.
cathode lamp through the plasma (e). The excitation capabilities of the laser
plasma can also be increased through the use of auxiliary power sources that
remotely pump energy into the plasma initially established by the laser pulse
(f). Both microwave (14) and CO 2 -laser (15) pumping have been demonstrated.
Microwave energy can also be introduced by generating the LIBS plasma on
the sample in a microwave cavity (g) (16).
The ability to enhance emissions from elements in the LIBS plasma is an
important development because it promises to increase detection capabilities,
thereby increasing applications. Some of these enhancement methods, however,
introduce complexity that compromises the LIBS advantage of simplicity. The
simplest enhancement scheme is double-pulse LIBS in which the two pulses are
derived from the same laser and used in the collinear arrangement (Figure 2(b)).
Enhancements here are typically ∼10×, although for some elements, values
of >50× have been achieved (17). On the other hand, greater enhancements
(∼100×) can generally be achieved using the orthogonal pulse arrangement
(Figure 2(c)) (10), which, however, is not suited for some applications such
as standoff analysis. It should be noted that the enhancements achieved with
double-pulse LIBS in either configuration are element and matrix dependent
(10).
Another advantage of the laser plasma is that it is a robust excitation
source that can be generated in difficult environments to sample directly all
types of materials. The plasma can readily be formed in air and other gases at
sufficiently high pressures to produce breakdown. The plasma can be formed
on solid surfaces present in high- (e.g., 90 atm demonstrated) (18) and low-
pressure (e.g., 2 × 10−5 torr) (19) atmospheres to record useful spectra, although
the appearance of the spectrum changes significantly with the pressure along
with the optimum values of analysis parameters such as delay time. In one
application, LIBS has been used to monitor successfully the carbon content in
fly ash in a power plant under conditions of high temperature/high pressure (30
atm) (20).
The spark can also be used to analyze bulk liquids, solids submerged
in liquids, particles suspended in liquids, and dissolved impurities (21). The
spectrum generated by a single laser plasma on a solid immersed in a liquid
is typically very weak, requiring an alternate sampling method. For example,
a collinear double-pulse LIBS method can be employed in which the first
pulse forms a gas bubble at the surface and the second pulse forms a plasma
on the solid surface, thereby mimicking the formation of the plasma in air.
Alternatively, single laser pulses and an air purge at the solid surface can be used
to record useful spectra. It has also been shown that double-pulses can enhance
the detection of some but not all elements present in high-pressure (∼272 atm)
aqueous solutions (22). Although useful plasmas can be generated in these
different environments to monitor elements in particles, solids, and dissolved
materials, the optimal operating parameters must be determined individually
for each specific case.
Limitations
Although a unique excitation source, the LIBS plasma has some limitations that
become important because of the difficult environments in which the source
is often deployed. In these environments it is not always possible to control
many operational parameters to maximize LIBS analytical capabilities. The
mass ablated and the characteristics of the resultant laser plasma, for example,
are strongly dependent on operational parameters, including lens-to-sample
distance, laser pulse power density, and characteristics of the surrounding at-
mosphere (pressure, composition). Changes in these parameters affect analyte
signals as well as the relative intensities of emission signals thereby compro-
mising quantitative analysis and the successful identification of materials via
element ratios. To be sure, conventional sources for atomic emission spec-
troscopy are also sensitive to operating parameters but because LIBS is often
applied to the more difficult analysis problems, the effects of such changes on
the analytical results become evident and must be evaluated and remediated as
much as possible.
Although LIBS is usually deployed in the open atmosphere, there are
applications in which the ambient pressure may be significantly below or
above 1 atm. The more esoteric applications pertain to space exploration with
environments characterized by low (e.g., Mars) (23, 24), very low (e.g., surface
of the Moon, asteroids), and very high pressures (e.g., Venus) (18). Figure
3 shows the strong dependence of Si(I) and Mg(II) emissions (basalt rock
sample) on ambient air pressure as the pressure is reduced below about 10
torr. Figure 4 shows how the LIBS spectrum of a complex sample (basalt rock)
changes with pressure between 580 torr and high vacuum. Many emission
lines are reduced in intensity significantly (e.g., Mn(I)) or disappear (e.g.,
Ti(I)) as the pressure is reduced and only the more strongly emitting, higher
concentration species are observed at the lower pressure. In addition, at the
lower pressure, emissions from certain species become apparent (e.g., O(II)
and Si(II)) that are not observed at higher pressures. On the other hand, as
shown in Figure 5, as the pressure increases significantly above 1 atm., the
emission lines from a basalt rock remain but some lines broaden significantly,
complicating identification of certain emission features. These results show
that the LIBS plasma can be generated under extremes of conditions but that
the character of the spectrum changes significantly and that alternate analytical
lines may be required and that calibration for quantitative analysis will be
complicated.
The ability of LIBS to interrogate small areas and ablate microgram masses
or lower is valuable for micro-analysis applications (9). On the other hand, the
minute mass involved in a single LIBS measurement becomes problematic for
analysis of bulk materials, especially those that are inhomogeneous. Consider,
for example, that an XRF (X-ray fluorescence) instrument, a main competitor
to LIBS in some applications, has an active interrogation area of 1 cm2 , X-rays
Figure 3. Dependence of LIBS signals from Si(I) and Mg(II) in a basalt rock for
different ambient pressures.
that penetrate to a depth of 0.5 mm (matrix dependent), and an analysis time of

20 s. In this case, the volume of material interrogated is 0.05 cm3 corresponding
to a mass of 0.14 g for aluminum metal. In the case of the laser spark, if 200
sparks are formed on an aluminum target over 20 s and each spark ablates
1 µg of material, then the total mass of material ablated sums to 0.0002 g—a
factor of 700 less then the mass interrogated using XRF. In actuality, the mass
Figure 4. Comparison of LIBS spectrum of basalt at 580 torr (black line) and 0.0003
torr (gray line). Lines due to O(II) and S(II) appear at the lower pressure, whereas some
other lines disappear (e.g., Ti, 397–400 nm) that are observed at the higher pressure.
150000
0.77 atm.
Ca(I)
100000
Ca(II) Al(I) Ca(II)
50000 Mn(I) Fe(I)

Si(I) Sr(II)
Ti(I)
0
signal (counts)
385 395 40 5 4 15 42 5
150000
90 atm.
100000
50000
0
38 5 3 95 40 5 4 15 42 5
wavelength (nm)
Figure 5. Comparison of LIBS spectra of basalt at pressures of 0.77 and 90 atm.
interrogated by LIBS will actually be less because not all of the ablated mass
is vaporized and therefore analyzed by LIBS. In this example, XRF has a clear
advantage in terms of determining the average concentration of elements in a
bulk sample.
The two main steps in a LIBS analysis, ablation to produce atomized
material followed by excitation of the atoms, are dependent not only on the
laser and sampling parameters but also on the chemical and physical properties
of the sample (25, 26). An example of a physical matrix effect can be seen in
comparing calibration curves for the detection of particles of different sizes (27).
As the particle size increases beyond a certain threshold value, that value being
the maximum particle size that can be vaporized for a given laser pulse energy,
the slope of the calibration curve decreases significantly (∼6×) compared
to the calibration curve corresponding to smaller particle sizes. A chemical

matrix effect can be observed by comparing calibration curves for Mn in a
soil and clay matrix. The curve for Mn in soil has been shown to be greater
(∼6×) compared to the curve for Mn in a clay matrix (28). Interestingly, as the
ambient pressure is reduced, the two calibration curves approach each other
and merge at a pressure of about 0.05 torr. To be sure, such matrix effects
exist in other plasma sources for atomic emission spectroscopy such as the
ICP (29), but because of the high density of materials within the small laser
plasma, the effects are often more severe. Methods to ameliorate matrix effects
in LIBS are very important for quantitative analysis and these are discussed
below.
Safety Considerations in the Use of the Laser Spark
Certain precautions must be observed that are unique to the LIBS method
as a source for atomic emission spectroscopy and some of these can limit
its application. First of all, because the plasma is generated by a Class IV
laser, care must be exercised in deployment because this laser light represents
an ocular and skin hazard (30). Careful packaging and interlocking of some
LIBS instruments (e.g., those into which a sample is inserted) can reduce the
potential exposure hazard to near zero, making these instruments as safe to
operate as current conventional analytical instruments. There is some emphasis
on developing “eye safe” lasers (e.g., λ ∼ 1.54 µm) that will reduce the extent
of the laser nominal hazard zone (NHZ), but it is reasonable to assume that at
least for the foreseeable future LIBS will not become eye safe for applications
such as open path standoff analysis because of the high laser powers needed
to generate a robust plasma at distance. In these applications, administrative
and engineering controls can limit the hazards but the use of such interrogation
schemes in applications where the exposure potential cannot be eliminated will
not be feasible.
The laser spark can act as an ignition source for certain solvents and
mixtures of air and combustible gases (e.g., methane). For this reason, the use
of LIBS in certain situations (e.g., grading of ores in underground mines) will
be questionable and the use of LIBS with combustible or pyrophoric materials
(e.g., uranium) must be carefully evaluated. Also, the action of the laser pulse
on a solid material during LIBS analysis serves as a source of fine, respirable
airborne particles. Although the mass ablated by one pulse is typically in the
range of tens of nanograms to a few micrograms, repeated ablation at even 10
Hz repetition rates can lead to concentrations of airborne material that exceed
maximum permissible levels for some materials. Consider beryllium, with a
short-term exposure level ceiling of 10 µg/m3 . If 0.1 µg is ablated per pulse,
then after only 100 shots the ceiling limit in the vicinity of the ablation would be
exceeded. In these cases consideration must be given to the sampling protocol
and proper steps must be taken to prevent contamination of equipment and to

limit the exposure of operators and area personnel to harmful particles.
UNIQUE CAPABILITIES OF THE LASER PLASMA TO SAMPLE

MATERIALS
Because the laser plasma is formed by laser light, a number of sampling options
are possible using LIBS. These are illustrated in Figure 6. In situ sampling or
focusing the laser pulses on the target at short range (cf. Figure 2(a)) is the
simplest, most common form of LIBS sampling. For applications in which
access to the target may be restricted for a number of reasons (e.g., harsh
environment, limited physical access), laser pulses can be transported over
many tens of meters by a fiber optic to generate the laser plasma remotely
(31). The plasma light can then be collected by the same fiber or a second
fiber and then routed back to the detection system. Remote fiber optic LIBS is
especially valuable for applications in which there is not a clear line of sight to
the target or the propagation of open path laser beams is not feasible. Fiber optic
delivery has typically been used for the analysis of solids, although recently
the generation of an air spark using a short length hollow core fiber has been
demonstrated opening up some exciting new applications (32).
Standoff or long open path LIBS analysis is currently a popular topic,
due in part to its potential use to monitor the CBRNE (chemical, biological
radiological, nuclear, and explosive) threat associated with WMD (weapons of
Figure 6. Methods of interrogating a sample using LIBS. L = laser; S = spectrograph;

T = telescope; FOC = fiber optic; BI = beam injector for laser pulse into fiber; BE =
beam expander; FL = femtosecond laser; CC = chirp control.
mass destruction) (33–36). There is obvious value in being able to detect such
threats at a safe distance using either manned or robotic vehicles. The ability to
rapidly scan large areas from a fixed location is also attractive from a concept-
of-operations point of view. Using conventional LIBS in which the laser pulses
are focused on the remotely located target by a telescope arrangement, distances
of 45 m have been achieved using moderate sized laser systems (37). For longer
distances, LIBS has been demonstrated using the filaments generated in air by
femtosecond (fs) lasers. These filaments can be projected over distances of tens
to hundreds of meters with the location of filament formation determined by
controlling the chirp of the spectrally broad fs-laser pulse (38). The filaments
provide a method of transporting the laser pulse energy over long distances with
good efficiency compared to focusing with conventional LIBS focusing optics.
When the filament strikes a solid object, a plasma is formed that can be used
for LIBS analysis. The use of fs-filaments for standoff LIBS was demonstrated
by Rohwetter and coworkers (39) at a distance of 180 m using a copper metal
target. They also discuss the feasibility of extending the range for filament-
based LIBS to 1 kilometer and what would be required of a suitable detection
system.
In keeping with the application of standoff LIBS for CBRNE threat de-
tection, the use of IR and UV filaments to detect dinitrotoluene (DNT) and
ammonium perchlorate on aluminum and copper surfaces was demonstrated
in preliminary work (35). The infrared filaments produced an overall high
background due to their intense white light emission with atomic emission pri-
marily coming from the substrates. The UV filaments exhibited a much lower
background with reproducible spectral signatures coming from the explosive
regardless of the metal substrate. UV filaments have also been used to remotely
monitor targets related to cultural heritage (40).
Although filaments can be used to generate the LIBS plasma at long stand-
off distances compared to conventional LIBS focusing, there are no substantive
data at present to compare detection capabilities of the two methods.
Table 2 presents a summary of the advantages and disadvantages of each
LIBS sampling method shown in Figure 6.
QUANTITATIVE ANALYSIS USING LIBS
The objective of any quantitative analytical technique is to determine the

amount or concentration of an analyte accurately. Typically, this usually in-
volves developing a calibration curve that relates the amount of analyte (con-
centration or mass) to the observed analyte signal. As already noted, many
variables can affect the LIBS signal; the laser pulse energy and repetition
rate, the focusing method, the lens-to-sample distance (LTSD), detector pa-
rameters, and sample matrix. Depending on the application, some instrumental
parameters can be held constant during data collection to maximize analytical
Table 2. Evaluation of four LIBS sampling methods

Sampling
method Advantages Disadvantages
In situ Simple optics; low pulse Requires line-of-sight to target

energies; efficient light
collection; strong coupling
into all materials (opaque
and transparent);
interrogates gas, liquid,
solid samples; small spot
sizes for micro-analysis;
can accommodate
orthogonal double-pulse
LIBS
Remote (with Analysis at long distances; Upper limit to pulse energy to prevent fiber
fiber optic) does not require direct line damage; fiber transmission degrades
of sight to sample; path optical quality of laser light at distal end;
shielded from Class IV fiber probe must be positioned close to
laser light; low pulse target
energies compared to
standoff for same distances;
more efficient light
collection compared to
standoff methods;
interrogation of liquid and
solid samples; generation of
air spark using short length
hollow-core fibers
Standoff No physical intrusion into Requires line of sight to target; ocular
(conventional target area; ability to hazard due to open path to target; higher
focusing) rapidly acquire new targets laser powers and more efficient detection
using pan/tilt aiming system needed as standoff distance
system; rapid area analysis; increases; analytically useful plasma may
instrument can be located a not be formed on all materials at distance
safe distance from (e.g., samples transparent at the laser
hazardous locations wavelength); path of laser pulses to
sample affected by scattering and
absorbing species in the atmosphere
Standoff Same as for standoff Requires more complex fs-laser system;
(fs-filaments) (conventional focusing); requires line of sight to target; ocular
longer standoff distances hazard due to open path to target; more
achievable than for standoff efficient detection system needed as
using conventional standoff distance increases; analytically
focusing; precise focusing useful plasma may not be formed on all
on sample surface not materials at distance (e.g., samples
required transparent at the laser wavelength); path
of laser pulses to sample affected by
scattering and absorbing species in the
atmosphere
performance. In this case, a major factor affecting LIBS quantitative results is

the sample matrix. Ideally, the standard samples used to prepare the calibration
curve should be matrix matched to the unknown sample. This requirement
occurs because ablation to produce atomized material and the excitation prop-
erties of the laser plasma are both strongly dependent on the chemical and
physical properties of the sample as noted above (26). Unfortunately, in the
majority of situations, it is impossible to know definitely the composition of
the matrix of the unknown sample and even if the matrix were known, it is
unlikely that representative calibration standards would be readily available.
Much work has been done to resolve sample matrix issues with LIBS. One
approach has been the calibration-free method (CF-LIBS) that assumes local
thermodynamic equilibrium (LTE) in the plasma allowing for the calculation of
the plasma temperature and electron density from which the elemental compo-
sition of the sample can be determined. This method has several disadvantages:
an accurate plasma temperature and electron density must be determined, emis-
sions lines of all elements in the sample must be monitored, and the oscillator
strengths of the lines must be known to good accuracy. CF-LIBS has been used
on siliceous soils and rocks with method validation accomplished by using
NIST standards. For most elements, the percentage accuracy ranged from a
couple of percent up to 30%; this study showed the potential for LIBS as a first
search option for mineral analysis (41). Other studies have shown similar per-
centage accuracy when using this calibration-free method (42–49). Comparison
of the typical calibration curve method and CF-LIBS on ancient bronze coins
was carried out by Colao et al. (48). This study showed that the methods only
partially agree with each other. The typical calibration curve method predicts
lower concentration for copper, whereas CF-LIBS predicts lower concentra-
tions for zinc and tin. It is noted that the coins may have high compositional
nonhomogeneity, surface oxidation, and fractional and preferential evaporation
of the alloys, which could account for some of these differences.
A new method that uses a combination of the calibration-free and the
typical calibration method has been developed called controlled calibration
LIBS (42). This method determines the concentration of an element with the use
of a reference element. The use of this reference element negates the issues of
the sample matrix, the detection of spectral lines of all analytes in one spectrum,
and the determination of the factor, F, which is used to normalize the sum of the
concentration of the species in the CF-LIBS method. The determination of the
factor F is usually the source of inaccuracy in the calibration-free method. In the
controlled calibration method, the analyte concentration is determined by the
analyte and reference spectral lines and this produces a more accurate result.
In the study, a soil sample was analyzed with both the calibration-free method
and the controlled calibration methods using an ICP comparison for both of
methods. The controlled calibration method more closely matched the ICP data
with an average of 3.2% difference compared to the calibration-free method
with an average of 6.0% difference. Results from this study of the controlled
Table 3. Comparison of controlled calibration and calibration-free method with the

ICP (42)
Accuracy of
Controlled calibration Calibration-free
calibration-free
to accuracy of
ICP∗ Result % Difference Result % Difference controlled
Element (%w/w) (%w/w) from ICP (%w/w) from ICP calibration
O 46.99 46.65 0.72 48.85 3.96 5.47

Si 34.118 33.49 1.84 35.07 2.79 1.52
Al 6.13 6.35 3.59 6.65 8.48 2.36
Fe 2.87 2.56 10.80 2.68 6.62 0.61
Ca 0.536 0.543 1.31 0.569 6.16 4.71
Mg 0.534 0.562 5.24 0.589 10.30 1.96
Ti 0.516 0.504 2.33 0.528 2.33 1.00
Mn∗∗ 465 460 1.08 482 3.66 3.40
Pb∗∗ 210 210 0.00 220 4.76 NA
Cr∗∗ 80.5 85 5.59 89 10.56 1.89
∗
ICP: Results of sample analysis checked by Nanjing Soil Institute of Chinese
Academy of Science.
∗∗
These are the trace elements in the soil given in ppm rather than %w/w.
calibration method are replicated with some additional data calculations in

Table 3. On average, the controlled calibration data are about 2.6 times more
accurate than the calibration-free data (when compared to the ICP) (42).
Other approaches use chemometrics to analyze the entire LIBS spectrum
at once. Most of these methods employ principal component analysis (PCA),
soft independent modeling of class analogy (SIMCA), partial least squares-
discriminant analysis (PLS-DA), partial least squares regression (PLSR), and/or
neural networks. These methods can classify unknown compounds into their
proper classes and calculate concentrations of the analytes depending on how
the model is designed (50–52).
PCA calculates principal components (PCs), which are linear combinations
of variables that represent the majority of the information within the data
subset. For LIBS, the spectra are extracted in linear combinations of the PCs;
their coordinates along the PCs (scores) are used to show similarities and
differences between the spectra and can group them into their proper classes by
analyzing the scores and PCs together. No prior knowledge is needed to group
the spectra into their class (50).
SIMCA computes a PCA model for the different classes of samples (called
the calibration set) and can identify the new samples based on their distance to
each model that represents the different classes. This method cannot classify
unknown sample spectra to an unknown class; this means that the original
calibration set needs to include all of the possible classes for sample identifi-
cation, making SIMCA not an ideal solution for field analysis (50).
PLS-DA is similar to PCA in that it produces linear combinations of the
components. The difference comes in how the scores are correlated. PLS-DA
correlates the scores to both spectral variance and inner-class variance. New
spectra would have their score calculated to determine the most probable class
based on a calibration set (50).
PLSR uses a set of calibrated samples to calculate a linear optimization to
create a numerical model between concentration and spectral line intensities.
It is optimized by a cross-validation procedure that omits one spectra and
then another systematically to determine the optimal number of regression
components. The prediction ability of the regression is accomplished via a
validation set that is analyzed separately from the calibration set (51).
Neural networks are used in many areas for pattern recognition in nonlinear
optimizations. Neural networks consist of neurons that receive a sequence of
inputs that are weighted. The weighted sum of these inputs is compared to a
threshold value and a nonlinear function is applied to calculate the output. In
neural networks, the neurons are arranged in layers to form the network. For
example, a three-layer neural network consists of an input layer, which in LIBS
would be the spectrum; a hidden layer, which is a free parameter; and an output
layer, which provides the final results. These neural networks are trained using
a calibration phase consisting of a representation of the samples to be analyzed.
The performance of these neural networks is monitored by a validation set (51).
One study focused on comparing three calibration methods for calculating
the chromium concentration in soil samples using a typical calibration curve,
PLSR, and a three-layer neural network (51). The results showed that the
neural network analysis provided the most accurate and precise data, whereas
the PLSR method showed the poorest results due to nonlinearity of spectral
lines and self-absorption in the plasma. This study focused on just one element
in various matrices and showed the potential use of neural networks for LIBS
data. Another study expanded on this idea and used neural networks to analyze
multi-elements found in minerals (52). Here the neural network was applied
successfully to various silicate rocks and was able to calculate concentrations
of seven elements simultaneously. The results were compared to XRF data and
showed on average a mean deviation of about 15%; a replicate of the data for
one of the mineral samples is shown in Table 4. Neural networks have shown
much potential for LIBS analyses regardless of the sample matrix (51, 52).
COMPARISON OF LIBS TO CONVENTIONAL ATOMIC EMISSION

TECHNIQUES
Although LIBS can interrogate samples under conditions not possible using
conventional analytical methods, questions still arise as to how LIBS analytical
Table 4. Comparison of concentrations (%w/w) for LIBS results using neural networks
and XRF on a mineral sample-DAK-34 (52)
Element/ LIBS neural

compound XRF network Deviation (%)
SiO 2 56.5 57.0 1

CaO 15.2 17.5 15
Al 2 O 3 11.2 13.7 22
Ti 2 O 3 0.75 0.77 3
MgO 5.86 6.2 6
MnO 0.08 0.10 20
Fe total 4.77 5.3 11
figures-of-merit compare to these other methods. In terms of detection limits,

it is sometimes difficult to compare LIBS values to established laboratory
methods because these methods chemically reduce the starting sample (e.g.,
a metal) to a solution in which the analyte concentration is in units of µg/L.
LIBS can certainly analyze these liquids directly but doing so can dilute the
concentration compared to the starting sample, lowering detectability for LIBS.
In addition, LIBS may exhibit a greater degree of detection for an element in
its native matrix (e.g., in soil) compared to diluting the element by reducing
the sample to a solution. In addition, the laser pulse couples more strongly, in
general, to a solid than into a liquid sample. In any event, it is still instructive to
compare detection limits of LIBS with more conventional analytical methods.
Atomic absorption (AA) is a laboratory-based technique that uses the
absorption of light to measure the concentration of atoms. The samples, usually
in liquid or solid form, are vaporized in a flame or graphite furnace to produce
free atoms. Flame-AA requires liquid samples that must be aspirated with
the gas flow into a nebulizing/mixing chamber to form small droplets before
entering the flame. Solid samples must be prepared with an acid digestion
method to produce a solution. The graphite furnace (GF) requires minimal
sample preparation, can accommodate any sample type, and is a more efficient
atomizer; the furnace dries the sample, ashes the organic matter, and vaporizes
the sample to produce free analyte atoms. A main disadvantage of this technique
is that it analyzes one element at a time (53).
As for LIBS, conventional atomic emission techniques require that the
sample be vaporized or atomized and the atoms be excited to higher energy
levels. For this reason, some advantages of LIBS (e.g., simultaneous element
detection) also apply to these methods. Excitation sources for atomic emission
include flame excitation, direct current plasma (DCP), inductively coupled
plasma (ICP), microwave induced plasma (MIP), and electrode arc and spark.
Of these excitation sources, ICP is the most commonly used (53).
The ICP is a high-temperature (7000–8000 K) plasma excitation source

that provides efficient ionization of the sample, which helps to minimize the
molecular interferences. The high-temperature plasma is generated in a flowing
stream of argon gas by radio-frequency energy that ionizes the argon gas. The
ICP can be viewed directly and used for atomic emission spectrometry or it can
be combined with mass spectrometry (MS). Samples for the ICP are typically
prepared with an acid digestion method, although direct laser ablation of solid
samples into the ICP is possible (53).
As noted above, XRF is another atomic emission technique that is a strong
competitor to LIBS in some applications that can be laboratory or field based.
In XRF, X-rays from either a radioactive source or tube are used to eject
inner core electrons from atomic orbitals of atoms. When an electron from
a higher energy level falls to fill the vacancy, a photon is emitted that has
an energy characteristic of the particular element. In XRF, little or no sam-
ple preparation is needed as for LIBS. XRF portable units are available but
suffer from the inability to detect elements with an atomic number below
12, can experience interference effects that can mask analyte elements, and
can only perform surface analyses (54). Although X-rays do penetrate small
distances below the surface (e.g., 0.5 mm but dependent on the matrix com-
position), because the method is totally nondestructive, deeper regions cannot
be interrogated as is possible using LIBS with repetitive sampling at the same
spot.
A comparison of detection limits obtained using LIBS, AA, ICP, and XRF
is shown in Table 5. Detection limits for laser ablation ICP-MS are not shown
Table 5. Comparison of detection limits for atomic detection techniques.
LIBS Flame-AA GF-AA ICP-MS XRF

Element (ppm) (µg/L) (µg/L) (µg/L) (ppm)
As 2.7–15 <500 <1 < 0.050 10–100

Ba 0.1–600 <50 < 1.5 < 0.005 50–150
Be 0.4–10 <5 < 0.05 < 0.050 ND
Cd 0.2–306 <5 < 0.03 < 0.010 50–150
Cr 0.2–2100 <10 < 0.15 < 0.005 10–100
Cu 0.004–544 <5 < 0.5 < 0.010 10–100
Hg 2–84 NL NL NL 10–100
Li 0.006–40 <5 < 0.5 < 0.020 ND
Mn 7.2–454 <5 < 0.06 < 0.005 10–100
Ni 0.01–540 <20 < 0.5 < 0.005 10–100
Pb 0.3–8000 <20 < 0.5 < 0.005 10–100
U 100–1000 <100,000 ND < 0.010 10–100
Zn 0.85–380 <2 < 0.01 < 0.02 10–100
Ref. (266) (267) (267) (267) (268)
NL = element not listed in the reference; ND = element not detected.

in the table but the method has detection limits extending down to parts per
billion (55). The detection limit ranges listed for LIBS and XRF consist of a
range of values for various sample types including bulk solids, powders, and
liquids. The detection limits reported for flame-AA, GF-AA, and ICP are for
liquid samples. Overall, ICP-MS has the lowest detection limits for methods
listed in the table followed by GF-AA and flame-AA. These three techniques
are laboratory based, so samples would be collected in the field and transported
back to the lab for analysis. Both XRF and LIBS are adaptable for field-portable
instruments and offer reliable data for many elements. In comparing detection
limits for LIBS and XRF, LIBS tends to have somewhat lower limits than XRF
for many elements.
From the above discussion, if laboratory-based measurements are accept-
able in terms of cost and time and the equipment is available, the more traditional
methods of AA and ICP and the ICP variants would offer the best analytical
results. For many field-based applications, however, LIBS and XRF would be
considered. A few studies have shown how the methods compare and how they
may be used to together for complementary analyses results (56–58). XRF
instruments come in many different configurations tailored, for example, for
the detection of lead in paint, elements important to mining and exploration,
geochemical analysis, and metal alloy identification. LIBS has been investi-
gated for these same applications and it will be instructive to compare the two
methods (Table 6).
MOLECULAR DETECTION USING LIBS
LIBS is typically viewed as an elemental analysis method because information

about the chemical form of the starting material is lost in the high-temperature
plasma. Many researchers have been working with LIBS, however, to show
that this technique can be applied for molecular identification of species at
least for pure materials. Figure 7 shows LIBS spectra of several organic ma-
terials showing similarities and differences. Clearly, the spectra for explosives
(TNT, RDX, and PETN) appear very similar, with some minor differences
between the intensities of selected lines. The LIBS spectra for plastic mold-
ing and wood also appear similar. Such spectra are the starting LIBS database
for molecular identification schemes aimed at identifying the parent material.
Methods to distinguish between spectra usually involve either analyzing the
whole LIBS spectrum or focusing on selected atomic lines; for organics these
atomic lines mainly include C, H, N, and O, which are ubiquitous in nature,
thereby complicating analyses of organic species. In addition, these elements
are not strong emitters compared to many metal atoms, leading to relatively
high detection limits for these materials. Furthermore, N and O present in air
at high concentrations can be excited by the LIBS plasma formed on a solid
Table 6. Comparison of LIBS and XRF for three applications.

Lead in paint detection
LIBS XRFa
Depth profiling Yes; ∼0.25-mm ablated per laser No; X-rays penetrate below surface
spark for 15–20 mJ pulses (269) and sampling depth depends on
element (tenths of millimeters
(Ca) and hundredths of
millimeters (Fe) deep)
Speed of analysis <10 s Few seconds
Sensitivity 0.23 mg/cm2 (269) ∼0.01 mg/cm2
Nondestructive Some destruction to surface; Yes
severity depends on number of
shots
Material identification
Clean surface Yes; or cleaning shots needed prior Desirable; can interrogate some
required to analysis distance below immediate surface
Speed of analysis Many samples/s ∼10 s/sample
Sensitivity Sufficient for all metals Sufficient for metals with Z ≥ 11
Standoff detection Yes, up to many tens of meters No; in situ method
Plastics Yes, using C, H, N, O ratios and Yes, using elements found in
elements used for plastics sorting pigments/flame retardants (Cl,
via XRF Br, Sb, Ti) and other elements
(Pb, Cd, Zn, Si, etc.) found in
plastics
Geochemical analysis and exploration
Representative Yes; or cleaning shots needed prior Desirable; can interrogate some
surface required to analysis distance below immediate surface
Speed of analysis Several seconds or tens of seconds ∼2–5 s/sample
depending on surface
homogeneity
Sensitivity Sufficient for minor and major Sufficient for major and minor
elements elements with Z ≥ 12
Standoff detection Yes, up to many tens of meters No; in situ method
All applications
Point detection Yes (<0.5 mm) No

Area detection Yes, with repetitive sampling over Yes, over an area ∼1 cm2 inherent
area to method
Size 0.04 m3 (backpack) + 1000 cm3 2000 cm3 single unit probe
(probe)
Weight 15–25 lbs. 1.7–3 lbs.
Power 50 W (laser on; 10 Hz laser rep. Minimal
rate)
Safety Class IV laser (ocular hazard) Radioactive isotopes (some
instruments)
a
Some capabilities relevant to XRF analysis were taken from the Website
http://www.niton.com.
12000 5000
TNT plastic molding
10000
4000
8000
3000
6000
2000
4000
1000
2000
0 0
200 300 400 500 600 700 800 200 300 400 500 600 700 800
12000 5000
RDX wood
10000
4000
Intensity (counts)
8000
3000
6000
2000
4000
1000
2000
0 0
200 300 400 500 600 700 800 200 300 400 500 600 700 800
30000 7000
PETN styrofoam
25000 6000
5000
20000
4000
15000
3000
10000
2000
5000
1000
0 0
200 300 400 500 600 700 800 200 300 400 500 600 700 800
wavelength (nm) wavelength (nm)
Figure 7. Comparison of LIBS spectra of three explosives (on silica matrix) and three
substrates.
surface. This is where chemometrics (59) can play a vital role by analyzing the
whole spectrum at once and comparing it to a database of compounds.
The current primary focus of much of this research is for homeland security
and military applications. The goal is to use LIBS to detect various chemical,
biological, and explosive or CBE threats as noted above. Recent work by
Gottfried et al. (36) showed real-time detection of chemical and biological
warfare agents at standoff distances of 20 m using a double-pulse LIBS system.
In their system, two high-energy 1064-nm laser pulses (∼275 mJ) separated by
a couple of microseconds were directed collinearly onto a surface. A library
was created for pure powders of various biological warfare agent surrogates
and for biological, environmental, and household interferents. Single-shot data
were collected on cardboard and adhesive tape surfaces and a linear correlation
method was used to analyze the data. Using a PLS-DA model, they were able
to distinguish chemical, biological, and explosive samples. The main issue was
false alarms from non-threat interferents and from the use of different substrates
(36). Overall, coupling LIBS with PLS-DA appears promising for explosive
detection, though care must be taken when designing the model (33, 36). An
advantage of using a double-pulse LIBS system is that it has been shown
to reduce the air background signature, which is important when analyzing
biological and chemical substances with LIBS (60). Other studies performed
using single-pulsed LIBS for close-up analysis showed that the use of an argon
flow displaced the air, allowing for better characterization of the explosive
residues (34).
Laser wavelength selection is an essential factor to be considered for field
applications. A 1064-nm (NIR) pulse has a very low maximum permissible
exposure (MPE), whereas the value for 266-nm (UV) pulse is much greater (30),
although it is unlikely that any standoff LIBS system will ever be considered eye
safe as discussed earlier. A comparison of 266-nm and 1064-nm pulses for LIBS
excitation was explored using plastics and one explosive. The results showed
greater signal intensities with less signal variation using the NIR beam because
of better coupling of the NIR wavelength into the plasma once it is formed. On
the other hand, the UV beam yielded more consistent plasma generation for the
different materials tested compared to plasma formation using the NIR beam.
The authors suggested that using double-pulse UV and NIR wavelengths might
be a viable option for explosive detection to enhance signal intensities (61).
In another study, standoff detection (40 m) and differentiation of energetic
materials was accomplished using a 266-nm beam from an Nd:YAG laser
in conjunction with a 10.6-µm pulse from a CO 2 laser (62); both of these
lasers have a much higher MPE than the 1064-nm Nd:YAG laser commonly
used for LIBS, thereby reducing the NHZ in field applications (30). The CO 2
laser pulse, nearly simultaneous in time with the 266-nm pulse, was used to
enhance the emission from the plasma formed by the UV pulse (Figure 2(f)). In
an additional study, high-energy 532-nm pulses were used to characterize two
nitrocompounds based on the O/N intensity ratios (63). This work is continuing
to classify other organic compounds using this method and also to apply a linear
correlation and principal components analysis for more reliable results.
The substrate on which the sample resides poses an issue with LIBS
analysis. Consider, for example, attempting to identify TNT, RDX, or PETN,
especially at low concentrations, deposited on one of the substrates of Figure 7.
Studies have been performed comparing signals from TNT on aluminum, glass,
and Delrin R
surfaces using femtosecond and nanosecond (ns) laser pulses. The
results showed that the ns-laser pulses excited primarily atomic lines, whereas
the fs-laser pulses excited primarily molecular lines. It was concluded that the
molecular lines recorded with the fs-pulses were due to TNT on the substrate
and the substrate composition determined the strength of the emission features
and whether or not substrate lines were present. More work is planned to better
understand this phenomenon (64, 65).
Biological aerosol detection using LIBS has also been considered. The two
focus points are detection of biological aerosols from other interferents and de-
tection of single particles. Results from Hybl et al. (66) indicate that PCA of
the LIBS data can be used to distinguish between the biological aerosols and
interferents. Single-particle analysis of a biological simulant was performed
successfully using a more sensitive LIBS air monitoring system (67). Selective
collection of spore aerosols was accomplished using a size-selective two-stage
impactor with analysis performed by LIBS. Using this method of collection, the
detection of spores was accomplished successfully when there was no other par-
ticulate matter present like diesel exhaust and protein mixtures, which caused
false negatives (68). There is still a great deal of research needed in order to ap-
ply LIBS for biological aerosol detection. For implementation, improvements
are needed to detect lower concentrations of the biological spores, to develop a
more robust statistical model for biological aerosol identification, and to build
a more sensitive LIBS instrument that can detect biological aerosols over high
background levels of interferent aerosols in urban environments (66–68).
In order to show that LIBS can be applied for field analysis of molecular
samples, studies must be performed analyzing mixtures of these compounds
with possible interferents. For example, if a series of laser pulses is interrogating
a suspect contaminated area, the laser pulse will not only be exciting the analyte
but also the surface and whatever else may be on that surface. Swiping the
surface with a suitable material to collect the contamination can be performed,
though this method will also lead to other issues in that most suitable swipe
materials contain C, H, N, and O. Also, most swipe materials must not only
collect the contamination but also trap it within the swipe; when a laser pulse
interrogates the swipe, the strong shock/pressure wave produced by the laser
pulse can dislodge material from the swipe over an area significantly larger
than the area directly interrogated by the pulse. This effectively reduces the
concentration of collected material on the swipe.
As the discussion above indicates, work is ongoing to investigate LIBS
for the detection of chemical, biological, and explosive materials. A successful
method must have high sensitivity for trace amounts of material at some dis-
tance, must provide positive identification, and must exhibit a low false alarm
rate (69). In the area of explosives detection, recent evaluations lead to the
conclusion that currently LIBS does not provide satisfactory performance (70).
Techniques competing with LIBS for molecular analyses include photo-
dissociation laser-induced fluorescence (PD-LIF) and Raman spectroscopy.
Both of these techniques have been used remotely for explosive analysis with
success. PD-LIF has been shown to detect the NO fragments in various ni-
trocompounds with reasonable signal-to-noise ratios (69). A gated Raman
instrument using 532 nm was constructed for the detection of explosives and
improvised explosive devices (IEDs); this instrument could detect relatively
small amounts of target compounds up to 30 m on various surfaces (71). The
authors suggest developing a UV-gated Raman system, which would greatly
improve the detection capabilities due to the more intense Raman signals ob-
tained using UV excitation.
In real-world scenarios, such as encountered in IED or bioaerosol detection,
other species will significantly complicate the analyses based solely on LIBS;
this has been shown in previous work and is discussed above. In order to get
more acceptable results, LIBS may have to be combined with another technique.
Coupling LIBS with Raman spectroscopy is a promising way to exploit the
advantages of each of these techniques for biological and chemical analyses.
Raman is a nondestructive molecular detection technique characterized by high
selectively for molecular identification. Studies have already shown that both
of these techniques can be used together to collect complementary atomic
and molecular data from a sample (72, 73). In addition, the combination of
LIBS and Raman would provide detection of the full CBRNE suite: CBE
(LIBS+Raman); RN (LIBS).
LIBS—A NICHE TECHNOLOGY?
As noted at the beginning of this review, LIBS has a wide range of potential
applications for many real-world analysis needs. Many of these needs cannot be
addressed using conventional analytical methods but may be uniquely solved
using LIBS. Many of these applications, however, are of specialized interest
and not suitable for large commercial markets. A few laboratory-based LIBS
instruments are offered commercially and there appears to be some success in
marketing these to a selected group of customers. Here, LIBS as a laboratory-
based analysis technique may fill a niche; for example, the need for a rapid and
relatively inexpensive method of screening samples and obtaining an initial
quantitative analysis. On the other hand, LIBS cannot be expected to replace
the more established techniques of AA and variants of ICP, which have across-
the-board better analytical performance.
In terms of industrial markets, LIBS has not made a significant inroad
at the present time in any particular application. A good overview of some
realized applications of LIBS in this area is presented in the review by Noll
et al. (74). These applications include metals and alloys processing, scrap
metal and plastic recycling, and certain monitoring needs required by nuclear
power generation and spent fuel reprocessing operations. Other applications
include process control verification for pharmaceutical manufacturing (75, 76)
and estimating material failure in pipes and welds by mapping the spatial
distribution of key elements (Fe, Mn, Cu, Al, Ti, and Ni) along the exterior
surface of the pipes (77). Currently, a commercial instrument is being offered
for the rapid testing of solid and oral dosage pharmaceuticals. It appears that for
the most part, however, that these applications are presently limited in practice
resulting in one or two installations of prototype instrumentation to demonstrate
the technology.
SUMMARY
LIBS is a versatile method of elemental analysis with potentially wide-ranging

applications. Although it cannot directly compete with established laboratory-
based analytical methods in terms of the usual analytical figures of merit
(detection limits, accuracy, precision), it has unique capabilities that permit,
for the first time in some cases, the analysis of materials under conditions not
previously possible. As an understanding of the laser-material-plasma inter-
action increases and new methods are developed to enhance LIBS analytical
capabilities both through improved data analysis methods and improvements in
instrumentation and techniques, we expect interest in the technology to increase
along with the number of realized applications.
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Induced Breakdown Spectroscopy (LIBS) Fundamentals and Applica-
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Laser-Induced Breakdown Spectroscopy-Capabilities and Limitations

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Applied Spectroscopy Reviews

ISSN: 0570-4928 (Print) 1520-569X (Online) Journal homepage: https://www.tandfonline.com/loi/laps20

David A. Cremers & Rosemarie C. Chinni

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David A. Cremers1 and Rosemarie C. Chinni2

Keywords: LIBS, laser-induced breakdown spectroscopy, laser plasma, atomic

Address correspondence to David A. Cremers, Applied Research Associations, Inc.,

range of potential applications is unequalled by any other analytical technique

restricted library of candidate samples. A good example is the sorting of techni-

WIDE RANGE OF APPLICATIONS OF LIBS

THE LASER PLASMA AS AN ANALYTICAL SOURCE

Table 1. Some recent studies of LIBS applications and plasma characteristics

Application Topic Refs.

Table 1. Some recent studies of LIBS applications and plasma characteristics

Application Topic Refs.

Animal tissues, Macronutrients in plants; prickly pear’s (131–135)

Table 1. Some recent studies of LIBS applications and plasma characteristics

Application Topic Refs.

depth profiling of coated super alloy; fs/ns

Table 1. Some recent studies of LIBS applications and plasma characteristics

Application Topic Refs.

Plasma characteristics Optical far- and near-field plasmas; ambient (245–265)

that penetrate to a depth of 0.5 mm (matrix dependent), and an analysis time of

50000 Mn(I) Fe(I)

Figure 5. Comparison of LIBS spectra of basalt at pressures of 0.77 and 90 atm.

to the calibration curve corresponding to smaller particle sizes. A chemical

Safety Considerations in the Use of the Laser Spark

and proper steps must be taken to prevent contamination of equipment and to

UNIQUE CAPABILITIES OF THE LASER PLASMA TO SAMPLE

Figure 6. Methods of interrogating a sample using LIBS. L = laser; S = spectrograph;

QUANTITATIVE ANALYSIS USING LIBS

The objective of any quantitative analytical technique is to determine the

Table 2. Evaluation of four LIBS sampling methods

In situ Simple optics; low pulse Requires line-of-sight to target

performance. In this case, a major factor affecting LIBS quantitative results is

Table 3. Comparison of controlled calibration and calibration-free method with the

O 46.99 46.65 0.72 48.85 3.96 5.47

calibration method are replicated with some additional data calculations in

COMPARISON OF LIBS TO CONVENTIONAL ATOMIC EMISSION

Element/ LIBS neural

SiO 2 56.5 57.0 1

figures-of-merit compare to these other methods. In terms of detection limits,

The ICP is a high-temperature (7000–8000 K) plasma excitation source

Table 5. Comparison of detection limits for atomic detection techniques.

LIBS Flame-AA GF-AA ICP-MS XRF

As 2.7–15 <500 <1 < 0.050 10–100

NL = element not listed in the reference; ND = element not detected.

MOLECULAR DETECTION USING LIBS

LIBS is typically viewed as an elemental analysis method because information

Table 6. Comparison of LIBS and XRF for three applications.

Point detection Yes (<0.5 mm) No

wavelength (nm) wavelength (nm)

LIBS—A NICHE TECHNOLOGY?

LIBS is a versatile method of elemental analysis with potentially wide-ranging

1. Cremers, D.A. and Radziemski, L.J. (2006) Handbook of Laser-Induced

8. Aguilera, J.A. and Aragón, C. (2008) Characterization of laser-induced

58. Pérez-Serradilla, J.A., Jurado-López, A., and Luque de Castro, M.D.