Vol. 26, No.

14 | 9 Jul 2018 | OPTICS EXPRESS 18794

Simple method for liquid analysis by laser-

induced breakdown spectroscopy (LIBS)
D. C. ZHANG,1,2,* Z. Q. HU,2 Y. B. SU,2 B. HAI,1,3 X. L. ZHU,1 J. F. ZHU,2
1,4
AND X. MA
1
School of Physics and Optoelectronic Engineering, Xidian University, Xi’an 710071, China
2
Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000, China
3
University of Chinese Academy of Sciences, Beijing 100049, China
4
x.ma@impcas.ac.cn
*
dch.zhang@xidian.edu.cn

Abstract: As a fast-developing technique for in situ multi-element analysis method, laser

induced breakdown spectroscopy - LIBS is, however, developing slowly on liquid analysis
due to some technical difficulties. We propose a new method, namely capillary mode, to
quantify the concentrations of the elements in solution using LIBS. A Nd:YAG laser with
repetition of 10 Hz were used to analyze the solution of Na2CrO4 and no any sample
preparation in measurements. The experimental results show that the splashing of liquid
induced by laser pulses is decreased significantly and the pollution of mirrors is avoided
effectively using liquid capillary mode. The results of quantitative analysis for liquid are also
improved than other method. The calibration curves of Cr and Na are well characterized by
straight lines and the regression coefficient values of the linear fit are better than 0.998. The
limits of detection (LODs) of Cr and Na are determined to be 28.9 mg/L and 1.0 mg/L in this
work, respectively. The experimental results show that the liquid capillary mode provides a
more practical and very simple approach to improve accuracy of quantitative element analysis
in liquids by LIBS technique.
© 2018 Optical Society of America under the terms of the OSA Open Access Publishing Agreement
OCIS codes: (300.6365) Spectroscopy, laser induced breakdown; (140.3440) Laser-induced breakdown; (300.6210)
Spectroscopy, atomic; (350.5400) Plasmas.

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1. Introduction
LIBS as a powerful tool for the fundamental studies on the interaction of laser beams in
materials has acquired great interest in recent years [1, 2]. It has demonstrated unique
 Vol. 26, No. 14 | 9 Jul 2018 | OPTICS EXPRESS 18796

versatility and capabilities for on-line composition determination, thus allows fast contact-less
analysis of almost any type of material and the possibility to adapt the technique to the special
requirements of diverse practical analytical problems [3, 4]. LIBS has been used for
qualitative and quantitative analysis of elemental compositions from much different types of
samples such as solid and gas, therefore attracts substantial attention nowadays for a wide
range of applications [5–7].
LIBS also has been applied to liquids analysis in some experiments and shown great
potential for in situ monitoring water in the environment particularly for sewage [8], for
online monitoring of the chemistry of slurry [9], mine drainage quality monitoring, impurity
in oil and water [10], the nuclear fuels industry [11, 12] and so on. However, the applications
of LIBS in liquid acquired less attention of researchers while investigations on solids and
gases are more broader [13]. The main reason is primarily attributed to the technical
difficulties encountered in performing LIBS in liquids [14–16]. When laser beam focusing on
the liquid surface, the shock waves can be produced, which give rise to the splashing of the
liquid [14]. If the laser beam is focused in the liquid, the bubbles are generated inside of the
liquids. Then, the bubbles could reach the liquid surface and large fluctuation could be
generated [16–18]. The fluctuation of the liquid surface influences both the intensity of laser
and the signal of emitted light collected by spectrometer, which can change the state of the
laser-induced plasma and increase shot-to-shot signal variation so that the reproducibility of
spectral measurements will be decreased. In addition, the optical components could be easily
polluted by the sputtering produced by laser ablated solution. It decreases the laser pulse
energy coupled with the target and the signal collected by spectrometer [19]. Thus, it is
necessary to clean the optical components frequently to remove accumulated matter ejected
and splashed from the liquid sample induced by laser pulses.
To overcome these problems, various experimental tricks such as bulk liquids [20], liquids
jets [12, 21], deposition of sample on filters [22] or freezing the solution [23] have been
proposed. A variety of experimental LIBS configurations have been employed to study liquid
surfaces by testing various energies, focusing and collection paths [24]. To avoid splashing of
liquid and improve the data reproducibility, the laser frequency is reduced to 1 Hz and even
lower [15,19]. In order to improve the stability of the liquid sample, the parameters of liquid
form such as flow rate of slurry [9] and liquid sheet thickness have been investigated [1].
Though the reproducibility and sensitivity can be improved by these methods, the efficiency
of data acquisition will be limited due to the sample preparing or using low laser repetition.
In this paper, a liquid capillary mode for liquid analysis by LIBS is introduced. The
experimental parameters were optimized. Then the chromium and sodium were analyzed
quantitatively in Na2CrO4 solutions by this method. The splashing of the capillary mode and
the reason for improving the accuracy of LIBS for liquid were explored.
2. Experiments
2.1 Instrumentation
The experiments were carried out with a Nd:YAG laser (Quanta-Ray Indi, Spectra-Physics,
USA) which can deliver up to 1800mJ at fundamental wavelength with a pulse duration of 10
ns and a repetition rate of 10 Hz. As mentioned previously [25], the UV laser is helpful to
decrease RSD in quantitative analysis of LIBS. Thus, the third-harmonic emission of
Nd:YAG is used in this experiment and the maximum pulse energy is up to 220 mJ. The
energy of the laser pulse is measured by an energy meter (3sigma, J45LP-MB, Coherent,
USA). The laser beam is focused on the sample using a quartz lens with 80 mm focal length.
Figure 1 shows a schematic drawing of the LIBS system. Plasma emission is collected by a
pair of plano-convex lenses which focus the signal to bifurcated fiber cable with a diameter of
0.2 mm. The fiber is mounted onto the entrance slits of a four-channel fiber optic
spectrometer (Avantes, Nethlans). The spectrometer is equipped with four holographic
gratings of 2400, 2400, 600 and 1200 g/mm for the spectra range 230~343 nm, 340~438 nm,
 Vol. 26, No. 14 | 9 Jul 2018 | OPTICS EXPRESS 18797

435~935 nm and 934~1082 nm, respectively. The spectra were recorded using a CCD
detector with 2 ms minimum acquisition gate width. For controlling the delay time between
detector and laser pulse, a versatile digital delay generator (DG645, SRS Inc. USA) is used to
trigger the laser and the spectrometer.

Fig. 1. The schematic setup of the LIBS system for liquid experiment (a) liquid capillary
mode; (b) bulk liquid mode (c) liquid jet mode.

2.2. Methodology
The capillary mode is different from liquid jet mode widely used in liquid analysis by LIBS.
Some investigations have shown that the particles produced by laser are mainly emitting
along the normal direction of the target surface [26, 27]. Thus, it will be help to avoid the
pollution of lens and to decrease the disturb for the coupling of laser with target when laser
beam emits on target surface with an angle between the normal direction of the target. As
shown in Fig. 1, a stainless-steel capillary is positioned with an angle less than 45 degree
between the laser beam and the axis of capillary. A shield cover with a hole larger than laser
beam spot is positioned between focus lens and capillary, which can avoid the pollution of
lens by residual splashing. The liquid sample is pumped from a container by a peristaltic
pump and then flowed to the capillary through a flexible tube. Finally, the liquid sample
ejects from the capillary and returns to the container. The laser pulses will be interacted with
liquid sample on a small hole in the wall of capillary. When a new capillary is mounted, the
distilled water should be used as a background sample. Laser pulses are focused on the wall
of capillary to ablate the wall firstly. After several laser pulses, the wall of capillary can be
penetrated with a hole of hundred micrometers. When the peristaltic pump is working, the
distilled water flows through the capillary. Meanwhile, a few parts of distilled water flow out
 Vol. 26, No. 14 | 9 Jul 2018 | OPTICS EXPRESS 18798

from the ablation hole and laser pulse can ablate the distilled water at the ablation hole. When
the elemental lines from stainless-steel capillary vanished in spectra, that means the ablation
hole is large enough. Then the distilled water can be replaced by target liquid to start
measurements.
2.3 Standard solution preparation
Cr is a common element in industrial waste water [28, 29]. A reliable Cr monitoring method
is helpful for the inspection of wastewater. For analyzing the content of Cr in liquid using
capillary mode LIBS, the standard solution is homemade by dissolving sodium chromate
(Na2CrO4) in distilled water of known volumes. However, sodium chromate deliquesce easily
in air [30]. Thus, sodium chromate should be backed firstly. A moisture meter is used to bake
the sodium chromate and the temperature is set to 130 °C. The variation of water evaporated
from sodium chromate powder with baking time is shown in Fig. 2. It can be found that the
content of water evaporated from sodium chromate powder is not changed after 70 minutes
baking. Then the standard solution containing 1000 mg/l Cr was prepared by dissolving 3.118
g sodium chromate to 1-liter distilled water. Other nine standard solutions with chromium
from 1 mg/l to 800 mg/l were prepared by diluted the standard solution with distilled water.
32
The content of water evaporated (%)

30

28

26

24

22

20

18

10 20 30 40 50 60 70 80 90 100
Baking time (minitues)

Fig. 2. The variation of the water evaporated from sodium chromate powder with baking time.

3. Results and discussion

3.1 Experimental parameters
2200
Na2CrO4
H I 656.28 nm

2100
Na I 588.99 nm
Na I 589.64 nm

2000
Intensity (Counts)

1900

600
Cr I 520 nm

400

200

0
510 540 570 600 630 660
Wavelength (nm)

Fig. 3. Typical LIBS spectrum of Na2CrO4 solution.

LIBS signal depends strongly on the delay time, laser pulse energy, accumulation of laser
shots and so on. The solution with 200 ppm Cr was used to optimize experimental
parameters. High signal-to-noise ratio (SNR) is helpful to decrease LOD. The delay time
between laser ignition and detector start acquiring is used to optimize for SNR usually [16,
31]. However, the intensity of line will decrease rapidly with delay time. Therefor the delay
 Vol. 26, No. 14 | 9 Jul 2018 | OPTICS EXPRESS 18799

time should be as short as possible if SNR is high enough. In this work, the delay time is 2 μs
for Na measurements. As it is known, the line intensity could be enhanced by increasing the
laser pulse energy. However, the saturation of lines will occur if the laser pulse energy is too
high [14]. Thus, 100 mJ pulse energy is used as maximum pulse energy in this work. A
typical spectrum of Na2CrO4 solution in the region of 510~780 nm is shown in Fig. 3.
According to NIST database, there should be three lines of Cr near 520 nm in this range. The
lines 520.60 nm of Cr I, 588.99 nm and 589.64 nm from Na I are observed. The lines of
520.60 nm and 589.99 nm are used for the analysis of Cr and Na, respectively.
For liquid samples, the quantitative analysis becomes not so well as for solid samples.
Because matrix effect becomes very important [32, 33]. Accumulation of laser shots is
usually used to reduce the shot-to-shot variation effects on emission [16] and the
reproducibility of data can be improved. To determine the optimum number of single-shot
spectra to be accumulated, the RSD of 10 individual spectra of Na I (588.99 nm) line intensity
is plotted as a function of the number of laser shots in Fig. 4. It is clear that the RSD value
decreases significantly by increasing the number of laser shots and then the RSD value will
be stable when the laser shots are more than 80 shots. 100 shots were chosen as one replica
for the calibration curves in this work.
30 Na 588.99nm
Delay time 3us
25

20
RSD(%)

15

10

0
0 20 40 60 80 100 120 140 160 180 200
Laser shots for one replica

Fig. 4. RSD of the Na (588.99nm) line peak intensity VS. the number of laser shots for one
replica.

3.2 Quantitative analysis

For evaluating the effect of capillary mode LIBS for elemental analysis in liquid, the
concentrations of Na and Cr in the solution of Na2CrO4 was measured. The result is also
compared with the results using bulk liquid mode [shown in Fig. 1(b)] and liquid jet mode
[shown in Fig. 1(c)]. Figure 5 shows the calibration curves of Na I by plotting concentration
vs. the net lines peak intensity of 588.99 nm with three different methods. As shown in Fig.
5(a), a fitting curve with very poor correlation is obtained by bulk liquid mode. It is hardly
used to quantitatively analyze liquid. As evident from the Fig. 5(b) and Fig. 5(c), the
calibration curves are well characterized by straight lines and the regression coefficient values
of the linear fit are better than 0.999 By comparing Fig. 5(b) with Fig. 5(c), it can be found
that the line intensity is higher and the deviation is smaller for liquid capillary mode than
liquid jet mode. The maximum RSD in Fig. 5(c) is less than 3%. In fact, for the liquid
capillary mode, all the regression coefficient values of the linear fit measured with delay time
from 0.5 μs to 4 μs are all better than 0.999. It should be noted that the calibration curve in
Fig. 5(b) or Fig. 5(c) is not a straight line, which indicates that the self-absorption of Na line
is presented when the concentration is higher than 200ppm [21, 34].
 Vol. 26, No. 14 | 9 Jul 2018 | OPTICS EXPRESS 18800

Fig. 5. Calibration curve by (a) bulk liquid mode, (b) liquid jet mode and (c) liquid capillary
mode.

To calibrate the curve of Cr more attention should be paid. The capillary is made of
stainless steel that including 18.0~20.0% chromium. When high pulse energy of laser was
used, the small dithering of laser beam could result in the interaction of laser with the
capillary wall. Thus, the line intensity of Cr from solution could be interfered by Cr from the
capillary. A smaller focusing spot of laser beam can be obtained by decreasing the pulse
energy. It can reduce the probability of laser pulses interaction with capillary greatly. But, the
line intensity of Cr will also be reduced. Thus, a short delay time is needed for Cr
measurements. The calibration curve of Cr in Na2CrO4 solution with 35mJ pulse energy at 1
μs delay time is shown in Fig. 6. Good correlation (R2 = 0.998) is obtained for quantitative
analysis of Cr. The result means that the capillary should be free from the elements to be
analyzed and the laser beam and capillary should be stabilized as far as possible for in liquid
capillary mode.
400
Cr 520.6nm
350 Linear fitting
Delay time 1us
300
Intensity (Counts)

250

200

150

100

R2=0.998
50

0
0 100 200 300 400 500 600 700 800 900 1000
Concentration of Cr (mg/l)

Fig. 6. Calibration curve of Cr by liquid capillary mode.

 Vol. 26, No. 14 | 9 Jul 2018 | OPTICS EXPRESS 18801

LOD is an important index for quantitative analysis of LIBS technique. The LOD can be
calculated according to the expression LOD = 3σB/s [33, 35], where σB is the standard
deviation of the background and s is the sensitivity given by the slope of the corresponding
calibration curve. According to calibration curves of Fig. 5(c) and Fig. 6, the LODs of Na and
Cr by liquid capillary mode are 1.0 ppm and 28.9 ppm, respectively. The result is a bit better
than that in laser jet mode and the LODs of Na and Cr are 2.1 ppm and 35.1 ppm respectively
by laser jet mode at its optimized parameters.
3.3 Discussion

Fig. 7. The arbitrary three moments of the target surface with different ablation mode.

To investigate the reason for the increase of signal intensity and the improvement of RSD for
quantitative analysis of liquid by the capillary mode, the behaviors of the liquid surface
ablated by laser pulses were observed with a setup shown in Fig. 7. A He-Ne laser was used
to irradiate the surfaces of target and the images of the liquid surface were recorded by a
camera. The three arbitrary moments of the target surface with different ablation mode are
shown in Fig. 8. Figure 8(a) shows the images with bulk liquid mode. Very large fluctuation
up to several millimeters induced by laser pulses can be observed. It changes the intensity of
laser on liquid target so that the plasma spectroscopy becomes unstable. The plasma emission
also could not couple to fiber well. Thus, the fluctuation of LIBS signal is very large. Figure 8
(b) shows the target images of liquid jet mode. It is clear that a liquid column is produced.
However, the liquid column is broken down absolutely by the laser pulses. It might influence
the coupling of laser pulses with the liquid target so that the intensity of lines is not very high.
In addition, it produces a very large liquid splash so that the liquid in the container is lost
obviously and the optics are easily polluted in experiment. Figure 8(c) shows the target
images of liquid capillary mode. It can be found that very few liquid splashes ejected around
the ablated hole and the ejecta was mainly along the normal direction of capillary. The rise of
the surface is also not observed. This means the capillary limited the fluctuation of liquid
surface induced by laser pulses effectively. Thus, the intensity of laser focused on the target
surface becomes very stable and it is easy to optimize the signal intensity as highest. The
ablation point of laser is always keeping near the wall of capillary so that the emission signal
coupled to optical fiber is very stable. The loss of liquid and the pollution of mirrors are
avoided effectively.
 Vol. 26, No. 14 | 9 Jul 2018 | OPTICS EXPRESS 18802

Fig. 8. Arbitrary three images of the target induced by laser pulses with three different modes
(a) bulk mode: red arrows indicate the laser beam position, the yellow dash lines are the
position of the original liquid surface and the blue arrows indicate the liquid bubbles; (b) liquid
jet mode: red arrows indicate the laser beam position, the yellow arrows are the position of the
liquid injector and the blue arrows indicate the liquid column; (c) capillary mode: red arrows
indicate the laser beam position, the yellow dash lines are the wall of the capillary and the blue
arrows indicate the liquid splash.

4. Conclusions and outlook

We introduced a liquid capillary mode for liquid LIBS analysis for the first time. It can be
found from our experimental results that the main advantages of the capillary mode are as
follows: (1) very good linear calibration curves and very small RSD can be acquired; (2) the
splashing of liquid induced by laser pulses can be decreased significantly and the pollution of
optical mirrors can be avoided with 10Hz Nd:YAG laser; (3) no any preparation for the liquid
sample so that it is very easy to handle and the whole analysis process is very fast.
In brief, our approach shows excellent reproducibility in experiments. It helps to decrease
RSD and increase the signal emission intensity, the reliability and reproducibility for
elements analysis in liquid by LIBS. The LODs were determined to be 1.0 mg/L and 28.9
mg/L for Na and Cr respectively. In the future, we will improve the sensitivity and evaluate
the effect for multiple elements analysis with the capillary mode in solution. This method has
very good potential in the analysis of industrial water, mineral waters, river water, seawater,
salt lake and so on.
Funding
National Natural Science Foundation of China (NSFC) (91536103); Fundamental Research
Funds for the Central Universities (XJS17025); Open Fund of the State Key Lab of Power
Systems.