Third International Symposium on Intelligent Information Technology and Security Informatics
Identification of Nutrition Elements in Orange Leaves
by Laser Induced Breakdown Spectroscopy
Mingyin Yao,Muhua Liu*,Jinhui Zhao
Optics-Electrics Application of Biomaterials Lab
College of Engineering
Jiangxi Agricultural University
Nanchang,China
e-mail :mingyin800@126.com
Abstract— Laser induced breakdown spectroscopy (LIBS) has
been used for the determination of the species and concentration
of elements in industries. However, there is less research for
LIBS analysis of agricultural and environmental samples. In this
work, a LIBS system has been evaluated for the determination of
nutrition elements in orange leaves. The experimental setup was
designed by using a Nd:YAG laser operating at 1064 nm (200 mJ
per pulse and 5HZ repetition rate) and an Avantes spectrometer
(200-1100nm wavelength range)with ICCD detector. The species
and relative contents were identified by LIBS spectra, which
belonged to qualitative analysis. The quantitive analysis will be
carried combining with routine analysis such as ICP-OES.
Keywords-LIBS;orange leaves; nutrition elements
I. INTRODUCTION
The identification of nutritive elements in plants is of
vital importance to evaluate the nutritional status of fruit trees,
crops, vegetables and other foliages. Either essential
macronutrients (N,P, K, Ca, Mg, S) or essential micronutrients
(Fe, Cu, Mn, Zn, B, Mo, Cl and Ni) play decisive roles in
plant nutrition and can affect crop yields or qualities when
they are not present in appropriate concentration levels [1]. By
the identification of the contents of the nutritive elements in
the plant leaves, one can estimate any nutritive deficiency or
surplus which can cause serious problems in plant growth,
quality, yield and appearance. For instance, the sprouts of
plant are slim and fragile, and the plants have fewer fruits due
to the deficiency of N element. The stems and leaves turn sap
green, grow flabbiness and flourish due to the surplus of N
element, which results in the suspending of florescence and
fruit, and the infection of plant diseases and insect pests [2].
In general, the identification of nutritive elements in most
routine laboratories requires sample pre-treatments such as
washing, drying and grinding with further wet acid
decomposition in open or closed systems. The most
recommended method for large routine analysis of the acid
digests is ICP-OES (inductively coupled plasma optical
emission spectrometer), due to its inherent multielemental and
simultaneous analytical capabilities [3]. For instance, the
macronutrients P,K,Ca,Mg,and S as well as the micronutrients
Fe, Cu, Mn, Zn and B can be determined in approximately 30
second in each acid digest. Besides, atomic absorption
This work was supported by a grant from National Natural Science
Foundation of China (No.30972052).
*Corresponding author:e-mail:suikelmh@sina.com
978-0-7695-4020-7/10 $26.00 © 2010 IEEE
DOI 10.1109/IITSI.2010.83
Lin Huang
College of Bioscience and Engineering
Jiangxi Agricultural University
Nanchang,China
e-mail: huanglin213@126.com
spectrometry, ICP-MS (inductively coupled plasma mass
spectrometry), atomic fluorescence spectrometry can be
successfully used for the determination of nutritive elements
[4-5].
All the above methods have been used for routine analysis.
However, the methods need complicated and time-consuming
pretreatment, in which the real-time detection can not be
implemented, and the secondary contamination of samples
appears easily. Laser-induced breakdown spectroscopy (LIBS)
is basically an emission spectroscopy technique where atoms
and ions are primarily formed in their excited states as a result
of interaction between a tightly focused pulse-laser beam and
the material sample [6]. One of the important features of this
technique is that it does not require any sample preparation,
unlike conventional spectroscopic analytical techniques.
Samples in the form of solids, liquids, gels, gases, plasmas and
biological materials [7-11] can be studied with almost equal
ease. In spite of the growing interest for LIBS in the recent
literature there are very few applications dealing with the
analysis of plant materials. A multi-elemental method for
direct solid analysis of plant leaves by LIBS was evaluated by
Sun et al.[12]for the determination of three macronutrients(Ca,
Mg and P),four micronutrients(Fe,Cu,Mn,and Zn)and Al.
NIST certified reference materials and mixtures of these
materials in different proportions were used for calibration.
In 2008, Lilian Cristina Trevizan et al. [13] proposed a
method for determination of macronutrients in plant materials
by LIBS, and they also proposed determination of
micronutrients in 2009[14]. Leaves of 11 plant species were
analyzed by the proposed LIBS system. The certified
reference materials and reference materials, such as bush
branches and leaves, cabbage, soya four, rice four, apple
leaves, peach leaves, wheat four and spinach leaves were used
for calibration. The materials were homogenized by using a
cryogenic mill prior to the analysis. At least ten spectra were
collected in different test portions of the sample pellet. For
comparative purposes, plant samples and certified reference
materials were analyzed by ICP-OES.
Oranges are the feature fruits in Jiangxi province of China,
and their production has become the backbone of farmers in
economy. Many peasants have preliminarily mastered the
growth technology of fruit trees. But they are puzzled with the
kinds and quantity of fertilization. The essential elements in
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plants can not be sufficed by immoderate fertilization. So, it is
very important to determine the nutrition elements of plants
for reasonable fertilization, which can serve for fruit growers
and yield requirement. The aim of this work is to show the
results of the determination the species and spectra intensities
of the nutrition elements in orange leaves by using a LIBS
system.
II. MATERIALS AND METHODS
A. Experimental samples
Ten orange leaves from tree specimen base in Jiangxi
Agricultural University were chosen as experimental samples.
Samples were dried in drying oven at 60℃ temperature, till
the mass the samples kept invariable. The species and spectra
intensities of the nutrition elements N, P, Ca, Mg, S, Fe, Cu,
Mn, Zn and Cl in samples were analyzed by LIBS.
B. Experimental Setup
The sketch map of setup used sees Fig.1.The Nd:YAG
(yttrium-aluminum-garnet) nanosecond laser (BeamTech,
Nimma-200) provides pulses of 10 ns duration at 1064 nm and
a repetition rate of 10 HZ. The laser beam is focused on the
surface of a sample using a single lens of 200 mm focal
length. Typical maximum pulse energies at the ablation
surface were 200 mJ/pulse. To have a fresh spot for each laser
shot, the sample is fixed on a move platform.
Nd:YAG Laser
Mirror
PC
Multi-channel spectrometer
Fiber Optics Lens
Fiber Smaple
Move platform of smaple
Figure 1. Experimental setup of LIBS
Relative intensity
Figure 2. LIBS spectrum of some nutrient elements in 200-317nm range
399
Optical emission from the LIBS plasma was collected by a
2 m steel encased multimode fiber (core diameter=400 um)
.This fiber was coupled to an eight-channel AvaSpec
spectrometer equipped with a 2048 pixel ICCD (intensified
charge coupled device) detector (AVANTES B.V., 2048-
USB2-RM) which provided complete spectra coverage from
200 to 1100 nm with a resolution of 0.09 nm at 200 to 317nm,
0.07 nm at 315 to 417nm, 0.06nm at 415-499nm,0.08nm at
497-565nm, 0.08nm at 563-673nm,0.12nm at 671-
750nm,0.13nm at 748-931nm,and 0.11nm at 929-1050nm.The
AvaSpec spectrometer was controlled by personal computer
(PC) running manufacturer-provided software. LIBS spectra
were acquired at a delay time of 1.28 us after the ablation
pulse.
For each sample 20 spectra were taken. Each individual
spectrum was accumulated over 100 laser shots. Spectra were
recorded continuously in order to keep the experimental
conditions as identical as possible for all samples. Under the
given experimental conditions, we can consider the line
intensity of an element is proportional to the relative
concentration of the element. The average of 20 spectra of
individual sample was extracted as the line intensity of the
element. Line intensities of elements in samples provide a
profile of relative concentrations of the elements.
III. RESULUTS
Fig.2 to Fig.5 shows a typical LIBS spectrum in different
wavelength range from orange leaves respectively. The line
intensity of an element is proportional to the relative
concentration of the element. Line intensities associated to the
elements for a given samples provide a profile of relative
concentrations of the elements. So the species and relative
concentration of the elements can be identified by the LIBS
spectra.
Relative intensity

Figure 3. LIBS spectrum of some nutrient elements in 415-499nm range

Relative intensity

Figure 4. LIBS spectrum of some nutrient elements in 748-931nm range

Relative intensity

Figure 5. LIBS spectrum of some nutrient elements in 929-1050nm range

400
 IV. CONCLUSIONS
In this paper, the characteristic spectra of nutrition
elements in orange leaves have been extracted by LIBS. The
results demonstrated that the species and relative contents of
elements in leaves can be identified by LIBS spectra. The
profile of relative concentrations of the elements can be
associated with their LIBS spectra. Such relative
concentrations can be precisely determined by LIBS. However,
the above methods belong to qualitative analysis; much
progress needs to be achieved before LIBS can be considered
as a practical quantitive analysis. Experiments are currently
underway in our laboratory utilizing several different samples
of leaves to address these problems combining with routine
analysis such as ICP-OES.
ACKNOWLEDGMENT
Authors are thankful to key laboratory of modern
agricultural equipment and technology (Ministry of
Education& Jiangsu province,Jiangsu University) for financial
support.
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