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Spectral analysis of Qinling Mountain rock using laser

induced breakdown spectroscopy
a b a a a a
W.F. Luo , X.X. Zhao , H.Y. Zhu , D.H. Xie , J. Liu & P.F. Jin
a
School of Electronic Engineering, Xian University of Posts and Telecommunications, Xian,
Shaanxi, China.
b
School of Physics and Mechanical and Electronic Engineering, Xian University of Arts and
Science, Xian, Shaanxi, China.
Published online: 21 Jan 2014.

To cite this article: W.F. Luo, X.X. Zhao, H.Y. Zhu, D.H. Xie, J. Liu & P.F. Jin (2013) Spectral analysis of Qinling
Mountain rock using laser induced breakdown spectroscopy, Journal of Modern Optics, 60:21, 1905-1909, DOI:
10.1080/09500340.2013.865803

To link to this article: http://dx.doi.org/10.1080/09500340.2013.865803

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 Journal of Modern Optics, 2013
Vol. 60, No. 21, 19051909, http://dx.doi.org/10.1080/09500340.2013.865803

Spectral analysis of Qinling Mountain rock using laser induced breakdown spectroscopy
W.F. Luoa , X.X. Zhaob , H.Y. Zhua , D.H. Xiea , J. Liua and P.F. Jina
a School of Electronic Engineering, Xian University of Posts and Telecommunications, Xian, Shaanxi, China; b School of Physics and
Mechanical and Electronic Engineering, Xian University of Arts and Science, Xian, Shaanxi, China
(Received 15 July 2013; accepted 10 November 2013)

The composition of Qinling Mountain rock is studied using laser induced breakdown spectroscopy for the first time.
Elements Ca, Mg, Cu, Fe, C, Na, Si, Al, Ti, K and Mn are identified qualitatively. Using an improved iterative Boltzmann
plot method, the electron temperature of 16,825 K is inferred with Ca I lines at 422.67, 428.30, 443.49, 445.48, and
585.74 nm, while the ionic temperature of 15,587 K is obtained with Ca II lines at 393.37, 396.85, and 370.60 nm. The
electron number density of 1.49 1018 cm3 is inferred from the Stark broadened profile of Ca I 422.67 nm averaged
Downloaded by [Anadolu University] at 22:28 24 December 2014

with 10 single spectra. The laser-induced rock plasma is verified to be in local thermodynamic equilibrium and to be
optically thin based on the experimental results.
Keywords: atomic emission spectroscopy; LIBS; plasma

1. Introduction alternate forms of elemental analysis. This is because the

The knowledge of rock composition is essential to a better
understanding of the formation of the geological history.
Currently, several techniques, such as chemical analysis,
atomic absorption spectrometry, X-ray fluorescence analy-
sis, inductively coupled plasma mass spectrometry, and so
on, have been used for the routine analysis of elements [1,2].
All these technologies adopt the way of collecting samples
and then returning for analysis in the laboratory, which is
either time-consuming or non-efficient.
With the laser, a luminous plasma will be created when
a high power laser pulse is focused onto a sample. Through
collecting the emissions from the atoms and ions in the
plasma, the elemental composition or the elemental concen-
trations in the sample can be determined. This technology is
called laser-induced breakdown spectroscopy (LIBS) [37].
LIBS has rapidly developed into a major analytical technol-
ogy with the capability of detecting all chemical elements in
a pulse, applicability to virtually all sample types, and a lack
of sample preparation [4]. Furthermore, because only opti-
cal access to the sample is needed, remote on-line analysis in
hostile and toxic environments becomes possible [6]. With
its own unique advantages, LIBS has been applied in many
fields, such as environmental applications, archaeological
materials and art objects, pharmaceutical products, medical
and biological applications, military and homeland-security
applications, and even future space exploration [8].
However, in spite of the advantages mentioned above,
LIBS suffers from poor reproducibility compared to
processes (ablation, atomization and excitation) involved in
plasma formations are quite complex and difficult to repro-
duce [5]. The main parameters affecting the performance
of LIBS results include the laser properties (laser intensity,
excitation wavelength, pulse duration), and the properties
of the target material (physical and chemical) as well as the
surrounding atmospheric conditions [9,10]. Although a lot
of experiments have been done to address these problems,
there is still no universal model to describe the laser-induced
plasma phenomenon and study of its basic mechanisms is
still a great challenge.
Sharma et al. [11] have developed an integrated remote
Raman and LIBS system for measuring both the Raman
and LIBS spectra of minerals with a single 532 nm laser
of 35 mJ/pulse and 20 Hz. Gondal et al. [12] used LIBS
to determine the trace elments in volcanic rock samples
collected from cenozoic lava eruption sites. Salle et al. [13]
used different methodologies for quantitative rock analysis
by LIBS in a simulated Martian atmosphere.
In the present work, the measurements are carried out
to study the characteristics of the 1064 nm laser induced
rock plasma. The size of the rock is about 10 cm 10 cm
and was collected from the Qinling Mountain in Xian,
China, and to our knowledge, there is no similar report
on the elemental study of Qinling Mountain rock using the
LIBS technique. The electron temperature and ionic temper-
ature are determined using an improved iterative Boltzmann
plot method with Ca I lines and Ca II lines, respectively.

Corresponding author. Email: luowenfeng@xupt.edu.cn

2014 Taylor & Francis

 1906 W.F. Luo et al.
The electron density is also inferred from the Stark broaden-
ing of the Ca I line at 422.67 nm. Based on the experimental
results, the experimental plasma is verified to satisfy the
LTE model.At the same time, some other plasma parameters
are also calculated.
2. Experimental
The experimental setup consists of a Q-switched Nd:YAG
laser (SGR, Beamtech Optronics), which delivers 135 mJ
per pulse at 1064 nm with 19.7 ns pulse duration, 10 mm
beam diameter and a frequency of 1 Hz. The laser beam
is focused onto the rock sample by using a fused silica
quartz lens ( f = 150 mm). The optical emission from the
rock plasma is guided to the AvanSpec-2048FT-5
spectrometer via a fiber bundle to yield information on
the elemental makeup of the Qinling Mountain rock. The
Downloaded by [Anadolu University] at 22:28 24 December 2014
AvanSpec-2048FT-5 spectrometer, triggered by the
Q-switch of the Nd:YAG laser, has five channels cover-
ing 200700 nm optical range, with the optical resolutions
of 0.06 and 0.08 nm. The spectrally dispersed signals are
automatically sent to an in-built charge-coupled device,
which converts the spectral signal into a digital signal. The
data averaged from 10 laser shots are stored in a personal
computer through AvaSoft-LIBS for subsequent analysis.
All the experiments are performed at room temperature in
air at atmospheric pressure.
3. Results and discussion
3.1. Description of plasma emission
Figure 1 represent the portions (200640 nm) of the av-
eraged laser-induced plasma spectra of Qinling Mountain
rock, in which almost all representative neutral and ionic
lines are visible. Experiments demonstrate that soon after
initiation, continuum, primarily due to free-free emission
and free-bound emission, is seen [4]. The continuum is the
white light from the plasma that contains little spectroscopic
information. As time progresses, continuum emission de-
creases, while the ionic and atomic emission lines become
dominant [4]. To obtain a good compromise between the
signal background ratio and the line emission intensity, a
delay time (5 s) from the ignition of the laser shot to
the opening of the window, during which signal will be
accepted, is chosen in our experiments. At the same time,
the integrated time of 2 ms is adopted.
With the help of the peak identification facility in the
AvaSoft-LIBS software and NIST database [14], some rep-
resentative atomic and ionic lines are identified and shown
by the arrows in Figure 1. For example, these lines are
as follows: Ca I 422.67, 428.30, 443.49, 445.48, 526.56,
585.74 nm; Ca II 393.37, 396.85, 370.60 nm; Fe I 279.55,
360.64, 406.19, 453.39, 455.45, 460.55 nm; Fe II 212.23,
220.84, 262.92, 438.60, 510.07 nm; C II 243.49 nm; Si I
251.55, 288.16, 298.76, 390.55 nm; Mg I 285.21 nm; Al I
308.22, 309.27, 394.40, 396.15 nm; Cu I 324.75, 327.40 nm;
Na II 251.55, 344.01 nm; Ti II 498.47, 499.18, 500.70,
532.39 nm; K I 404.72 nm; Mn I 403.30 nm. Thus, our
experimental results clearly demonstrate that the Qinling
Mountain rock at least contains these elements.
3.2. Determination of excitation temperature Te
The main factors that influence the light emitted by the
plasma are its temperature, the electron density and the num-
ber density of the emitting species [5]. Therefore, the knowl-
edge of the plasma parameters (electron density and electron
temperature) is important to understand the processes (dis-
sociation, atomization, excitation, ionization) during the
lasermatter interaction.
The spectroscopic determination of electron temperature
of the laser-induced plasma assumes that the local thermo-
dynamic equilibrium (LTE) exists which will be discussed
below. Under LTE, the number densities in various excited
states follow the Boltzmann distribution and their relative
intensity can be described as [6]
   
mn Imn Em N (T )
ln = + ln , (1)
hcgm Amn kTe U (T )
where mn is the wavelength, Imn is the intensity, h is the
Plank constant, c is the speed of light in vacuum, gm is
the statistical weight of the upper level, Amn is the tran-
sition probability, E m is the upper level energy, Te is the
electron temperature, k is the Boltzmann constant, U (T ) is
the partition function and N (T ) is the total number density
of species, respectively. Plotting the expression on the left-
hand side of the equation versus E m , a slope of 1/(kTe )
can be obtained, and the plasma temperature will be inferred
from the linear regression.
To calculate the electron temperature of the laser-induced
rock plasma, an improved iterative Boltzmann plot method
is used and a threshold value of 0.98 is set beforehand
[15]. After several iterations, the final result is shown in
Figure 2 with Ca I lines at 422.67, 428.30, 443.49, 445.48
and 585.74 nm. With the fitting slope, the electron temper-
ature of 16,825 K with the regression coefficient of 0.986 is
inferred. At the same time, the variations of the regression
coefficient and the electron temperature with iteration are
depicted in Figure 3. As a whole, as the regression coef-
ficient increases, the electron temperature becomes more
stable.
With the Boltzmann plot method, the ionic temperature
of the plasma is also inferred with Ca II 393.37, 396.85 and
370.60 nm. From the slope shown in the Figure 4, the ionic
temperature of 15,587 K is determined with a regression
coefficient of 0.991. It is apparent that these two temper-
atures equal each other within the uncertainty of 7%. Our
results further demonstrate that, under the condition of LTE,
the ionic temperature, excitation temperature and electron
temperature would have the same value corresponding to
 Journal of Modern Optics
(a)
(c)
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Figure 1. Segments (a,b,c,d) of the corresponding emission spectra of laser-induced rock plasma.
Figure 2. Boltzmann plot with Ca I emission lines in laser-
induced rock plasma.
the thermodynamic equilibrium temperature of the species
[46].
The corresponding parameters of the lines used in this
paper are presented in Table 1 [14].
3.3. Determination of electron density Ne
Electron density is an important parameter to establish the
equilibrium in laser-induced plasma [4]. One of the most
powerful spectroscopic techniques to determine the electron
density with good accuracy is obtained by measuring the
Stark broadening of emission lines of major species in the
plasma. This is because that, in low-temperature plasmas
of high density, the dominant broadening mechanism of
1907
(b)
(d)
Figure 3. Variations of correlation coefficient and plasma
temperature versus the iteration for Ca I emission lines in
laser-induced rock plasma. (The colour version of this figure is
included in the online version of the journal.)
the line profile is Stark broadening, which is relatively in-
dependent of the temperature [16]. The electric field that
causes the Stark effect in LIBS plasmas results primarily
from collisions with electrons, with small contributions due
to collisions with ions [4]. Therefore, the relation between
FWHM 1/2 (full width at half maximum intensity) of the
Stark broadening and the electron density can be expressed
simply as [17]
 
Ne
1/2 = 2w , (2)
1016
where w represents electron impact parameter [4] and Ne
is the electron density in the plasma.
 1908 W.F. Luo et al.

Table 1. Physical parameters for Ca I and Ca II transitions used in our experiments.

Wavelength (nm) E m (cm1 ) Amn (107 s1 ) gm
Ca I 422.67 23652 21.8 3
Ca I 428.30 38551 4.34 5
Ca I 443.49 37751 6.7 5
Ca I 445.48 37757 8.7 7
Ca I 585.74 40719 6.6 5
Ca II 370.60 52166 8.8 2
Ca II 393.37 25414 14.7 4
Ca II 396.85 25191 14 2
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Figure 4. Boltzmann plot with Ca II emission lines in Figure 5. Stark broadened profile of Ca I 422.67 nm in
laser-induced rock plasma. laser-induced rock plasma.

Figure 5 is the typical Stark broadened line profile of
Ca I 422.67 nm averaged from 10 single spectra in order to
smooth out the fluctuations of laser-ablated plasma intensity
and it is fitted fairly well with a typical Lorentzian profile
(R 2 = 0.85). With the fitting results, the electron density is
inferred to be 1.49 1018 cm3 considering instrumental
broadening.
3.4. LTE requirement
To determine the electron temperature, the plasma must sat-
isfy the equilibrium conditions. In a LTE plasma, the colli-
sional excitation and de-excitation processes must dominate
radiative processes and this requires a minimum electron
density [18]. A necessary but not sufficient criterion for LTE
is [16]
Ne (cm3 ) 1.4 1014 Te
1/2
(eV)[E(eV)]3 , (3)
where E (eV) is the largest energy difference between
the states for which LTE holds, and Te is the excitation
temperature. For all lines used, the largest energy difference
is approximately 3.34 eV, and the highest electron temper-
ature is approximately 1.44 eV. With these values, LTE is
satisfied for an electron density higher than approximately
6.21015 cm3 . As the electron density calculated is 1.49
1018 cm3 , LTE is valid under the present experimental
condition.
3.5. Optically thin
When estimating plasma parameters, it is also important to
ensure the laser-induced plasma ai free from absorption. A
plasma is said to be optically thin when the emitted radi-
ation traverses the plasma without significant absorption.
There are two relatively easy ways of checking the optical
thickness of a plasma. Considering the emission lines used
in our experiments, no evidently flat-topped profiles or dips
are found, which indicates that current plasma is free from
self-absorption and self-reversion [4].
Furthermore, other experimental methods can be used to
detect self-absorption. In the optically thin plasma, the in-
tensity ratio (I2 /I1 ) of two emission lines with the same up-
per energy level should be the same as the ratio of (Y2 /Y1 ),
where Y represents (g A/) according to the Boltzmann
law [19]. Take Ca I 445.48 nm, Ca I 443.49 nm and Ca II
396.85 nm, Ca II 393.37 nm for example. The observed in-
tensity ratio of ICa I 445.48 nm /ICa I 443.49 nm is approximately
 Journal of Modern Optics
0.7, which approximately equals the value 0.5 of
YCa I 445.48 nm /YCa I 443.49 nm . It is a similar case for Ca II
396.85 nm and Ca II 393.37 nm, i.e. ICa II 396.85 nm /
ICa II 393.37 nm is approximately 1.8 and YCa II 396.85 nm /
YCa II 393.37 nm is 1.6. Considering the experimental uncer-
tainty, the experimental plasma is optically thin.
4. Conclusions
In this paper, the elemental composition of Qinling Moun-
tain rock is first studied using the LIBS technique qualita-
tively. Based on its plasma spectra, elements Ca, Mg, Cu,
Fe, C, Na, Si, Al, Ti, K and Mn are identified. With Ca I lines
(422.67, 428.30, 443.49, 445.48 and 585.74 nm) and Ca II
lines (393.37, 396.85 and 370.60 nm), the electron tempera-
ture and ionic temperature of the rock plasma are inferred to
Downloaded by [Anadolu University] at 22:28 24 December 2014
be 16,825 and 15,587 K, respectively. At the same time, the
electron density is calculated to be 1.49 1018 cm3 using
the Stark broadened profile of Ca I 422.67 nm. With the
experimental results, the laser-induced plasma is verified to
satisfy the LTE model and to be free from self-absorption.
Acknowledgements
Author wants to thank State Key Laboratory of Transient Optics
and Photonics, Xian Institute of Optics and Precision Mechanics,
CAS.
Funding
This work is supported by Scientific Research Program Funded
by Shaanxi Provincial Education Department (2013JK0607,
2013JK0620), and by General Program Funded by Youth Founda-
tion of Xian University of Posts and Telecommunications
(ZL2013-14), and by Xian Science and Technology Planning
Project (CX12189WL02).
1909
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