Environ Monit Assess (2007) 124:131139
DOI 10.1007/s10661-006-9213-x
ORIGINAL ARTICLE
Measurement of nutrients in green house soil with laser
induced breakdown spectroscopy
T. Hussain M. A. Gondal Z. H. Yamani
M. A. Baig
Received: 29 September 2005 / Accepted: 17 February 2006 / Published online: 6 September 2006

C Springer Science + Business Media B.V. 2007
Abstract Laser-induced breakdown spectroscopy
(LIBS) has been applied for the determination of
nutrients in the green house soil samples. We deter-
mined appropriate spectral signatures of vital nutrients
and calibrated the method to measure the nutrients
in a naturally fertilized plot, cultivated with tomato
and cucumber plants. From the calibration curves we
predicted the concentrations of important nutrients
such as Ca, K, P, Mg, Fe, S, Ni and Ba in the soil. Our
measurements proved that the LIBS method rapidly
and efficiently measures soil nutrients with excellent
detection limits of 12, 9, 7, 9, 7, 10, 8 and 12 mg/kg
for Ca, K, P, Mg, Fe, S, Ni and Ba respectively
with a precision of 2%, The unique features of
LIBS for rapid sample analysis demonstrated by this
study suggests that this method offers promise for
precision measurements of soil nutrients as compared
to conventional methods in short span of time.
Keywords Laser-induced break down spectroscopy
(LIBS) . Continuous emissions monitoring .
T. Hussain . M. A. Baig
Institute of Environmental Science & Engineering,
National University of Sciences and Technology (NUST),
Tamiz Ud Din Raod, Rawalpindi, Pakistan
M. A. Gondal ( ) . Z. H. Yamani
Laser Research Laboratory, Physics Department King Fahd
University of Petroleum & Minerals Box 372, Dhahran
31261, Saudi Arabia
e-mail: magondal@kfupm.edu.sa
Nutrients and soil . Trace metals detection . LIBS
applications . Analysis of soil sample
1. Introduction
It is well known that inside a single farming field, an
agricultural producer may encounter with a variety of
soil types due to Non Uniform Distribution of Nutri-
ents (NUDN). Due to NUDN, the field may result in
over or under stress of nutrients and could embrace
inefficient allocation of resources. Precision farming,
also known as site-specific or prescription farming is
of growing interest among agriculturist and crop pro-
ducers (Paustian et al., 1992). This is due to the fact
that precision farming and management of nutrients
allows growers to optimize inputs of nutrients spe-
cially, Calcium, Phosphorus, Nitrogen, Sulfur, Iron and
Potassium, on a site-specific basis. The over-fertilizing
is also dangerous and can lead to environmental con-
cern such as runoff from green house farms and may
also affect the water table. Due to these facts, it is well
established that the Soils are naturally heterogeneous
(Parton et al., 1987). By identifying sites where there
is deficiency of nutrients in a field, farmers can create
management zones and treat these areas with nutrients
to enhance the crop yield. This is the reason that the
Soil quality and ecosystem productivity directly de-
pends on the uniform distribution and concentration of
the nutrient. Uniform distribution of Nutrients is the
fundamental building block of soil organic matter and
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it is a primary determinant of many soil chemical and
physical properties including soil structure, and water-
holding capacity, conductivity, porosity, pH and many
other factors (Lal, 1999; Paul et al., 2001). Once the
soil samples are analyzed then the analysis results could
guide the farmer for better identification or pin pointing
of fertilizer needs within a field. Many researchers are
presently investigating optimum soil testing methods
for precision agriculture. The efficient testing meth-
ods for measuring the concentration of nutrient are re-
quired for better estimates of crops yield and fluxes due
to their effective management and control.
Due to above mentioned reasons; development of
efficient methods of measuring nutrients is a press-
ing need to improve the quality of soil and produc-
tion yield. Over the past two decades, several ad-
vanced analytical methods have been developed to
study soil nutrients and other constituents. The com-
position of soil has been evaluated by new applications
of instrumental laboratory analyses (McCarty et al.,
2001; Radziemski and Cremers, 1989) and has been
quantified using infrared spectroscopy (McCarty et al.,
2001).
The Modern agricultural farm management need in-
novative methods/techniques for testing and analysis
of the nutrient concentration level. Even today, in un-
derdeveloped and even in advanced countries, many
farm house owners still collects samples of their field
and transport the sample to a laboratory and waits for
months for their soil test results. Most of these labora-
tories are based on conventional soil testing techniques
and require a lot of time due to sample preparation,
sample treatment with some acids and other modali-
ties. The farmers prefer a low cost, quick and precise
approach called smart sampling for testing their soil
samples. Soil test is essential to determine crop nu-
trients needs before applying any kind of commercial
fertilizer or manure.
Here we report some important results of an inno-
vative spectroscopic method for measuring the nutri-
ents that is based on laser-induced breakdown spec-
troscopy (LIBS). The instrumentation and operation of
a LIBS system is simpler than other conventional an-
alytical techniques and the analysis time of the order
of few minutes makes LIBS more amenable for ana-
lyzing nutrients in soil samples. The LIBS method is
based on atomic emission spectroscopy (Reid, 1997;
Cremers et al., 1996; Yamamoto et al., 1996; Cremers
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Environ Monit Assess (2007) 124:131139
et al., 1996; Radziemski, 2002). In this method, a laser
is focused on a solid sample and forms microplasma
that emits light characteristic of the elemental com-
position of the sample. The emitted light is collected,
spectrally resolved, and detected to monitor concen-
trations of nutrients via their unique spectral signa-
tures. When calibrated, the method provides quanti-
tative measurements. The method could be built with
low cost for field-portable instrumentation and pre-
cise analysis (Sjostrom and Mauchien, 1991; Song
and Sneddon, 1997; Lee et al., 1997; Abdellatif and
Imam, 2002; Adrain and Watson, 1984). We evalu-
ated the LIBS method for its potential to measure the
concentration of soil nutrients in green house sam-
ples collected from different locations of selected green
house plot. The development of the LIBS system for
environmental and other analytical applications such
as monitoring of nutrients in green house soil sam-
ples is a continuity of our group activities for devel-
opment of laser based pollution monitoring systems
like Photoacoustic (Gondal, 1997; Gondal et al., 2001,
2002, 2004) and LIDAR system (Gondal et al., 2000,
2002).
2. Experimental set up details
A Nd: YAG laser (Spectra-Physics Lasers, Model GCR
100) at a wavelength of 1064 nm (30-mJ pulses of 8 ns)
was focused with a lens of 30 mm focal length on each
soil sample (Fig. 1). The light from the plasma spark is
collected by a collimating lens using UV graded fused
silica 1 meter, multimode sampling fiber with SMA
connector and is transferred to LIB2000 + Spectrom-
eter (Ocean Optics). Our LIBS 2000 + has four spec-
trometer modules to provide high resolution (FWHM
0. 1 nm) in the 200 nm to 620 nm wavelength region.
The detector has a gated CCD camera having 14, 336
pixels. The emission is observed at a 45 angle to the
laser pulse. Software built in the spectrometer read the
data from the chip and reconstruct the spectrum. This
makes it possible to measure a large wavelength range
(200620 nm) simultaneously with high spectral reso-
lution (0.1 nm).
For each LIBS analysis a sample was placed on a
rotary table in a stain less steal cup of 20 mm diameter
by 10 mm long, then positioned such that the focal vol-
ume of the laser pulse was centered in the cup holding
Environ Monit Assess (2007) 124:131139
Fig. 1 Schematic diagram of the experimental set up used for recording the LIBS Spectra for green house soil samples
the sample. Twenty laser pulses were directed into the
cup to complete one measurement. The background
signals from carbon and silicon emissions were sub-
tracted from the resulting spectrum, and this procedure
was repeated for each sample. Because of shot-to-shot
variations in the laser plasma parameters and sampling
geometry, measurement precision is increased by ra-
tioning the analyzed signal to the signal from another
species, in this case silicon, with the same concentra-
tion assumed in all samples.
The nutrient concentrations from samples collected
from different locations from the green house sam-
ples was also measured by ICP and then used to ver-
ify the calibrated LIBS method against different sam-
ples from the same soils. The green house samples
were collected from five locations in the fields after
harvest of Tomato and Cucumber from 0 to 10 cm
and 10 to 20 cm below the soil surface. The sam-
ples were collected under tomato plants or cucumber
plants, or in inter canopy spaces that were either grass-
covered or bare. The results achieved with LIBS set
133
up were verified with the conventional method such
as ICP.
2.1. Sample preparation
A sample that accurately represents the soil area of
interest is a key in determining exactly the nature of
nutrients and their level in the green house farm. Soil
pH and nutrient level can be extremely variable due to
non-uniform distribution of lime, fertilizer and water.
Some nutrients are water-soluble. The greater the soil
moisture, the more they move. These mobile nutrients
include nitrate/nitrogen, sulfate/sulfur, and chloride-
which vary in importance with crop. So soil sampling
in green house need samples extended to 1020 cm
down in to the soil but at the same time some nutrients
are still available to the plants from the subsoil.
The soil sample was colleted from the marked lo-
cation of green house according to the standard proce-
dure in plastic bags and was stored carefully to avoid
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Fig. 2 Typical LIBS spectrum for the green house soil sample # 1
any type of mixing. As the mixing of the samples
can affect the results. These samples under investi-
gation were first sieved, dried and grinded in Spectro
Mill Ball Pestle Impact Grinder Model 1100-11 from
Chemplex industries, Inc 10707.USA to suitable mesh
size for preparation of Pellets. The pellets were made in
cylindrical form having diameter 20 mm and thickness
10 mm on hydraulic press of Carver laboratory Press
model C Sterling W/s 53051 USA. The applied load
was 12500 Pounds per square inch for fifteen minutes.
3. Results and discussion
We identified and quantified the nutrients and other
trace metals distribution within the green house using
LIBS technique.
3.1. Laser-induced breakdown spectra for
identification of nutrients
The method for making specific pellets from vari-
ous soil samples is described earlier under the sam-
ple preparation section. LIBS spectra of the pellets
made for five soil samples collected from different loca-
tions of green house were recorded in the 200620 nm
spectral region. Typical spectra of five samples indi-
cating the various nutrients used for their concentra-
tion are depicted in Figs. 26. The 255.32 nm emission
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Environ Monit Assess (2007) 124:131139
line of P (signature of P), 515.32 nm emission line of
Cu (signature of Cu), the 518.36 nm emission line of
Mg (signature of Mg), the 403.44 nm emission line
of Mn (signature of Mn), the 393.36 nm emission line
of Ca (signature of Ca), the 588.99 nm emission line of
Na (signature of Na), the 407.83 nm emission line of
Fe (signature of Fe), the 404.7 nm emission line of K
(signature of K), and the 547.92 nm emission line of
S (signature of S), have been selected for quantitative
analysis. The wavelengths of other elements present in
the soil sample are listed in Table 1. These emission
lines have minimal interference from other emission
lines, do not involve the ground state so that self- ab-
sorption is almost absent, and are intense enough. Due
to these reasons, these lines were selected for quantita-
tive analysis.
Before making the quantitative measurements about
the nutrient concentration, we optimized the experi-
mental parameters such as impact of incident laser en-
ergy, the time delay between the initiation of plasma
(arrival of the laser pulse) and the collection of plasma
emission (activation of the detector).
3.2. Influence of laser energy on nutrient intensity
The dependence of Nutrient signal intensity on the in-
cident laser energy for soil sample no. 4 is presented
in (Fig. 7). Here the LIBS signal for Ca 393.36 nm
Environ Monit Assess (2007) 124:131139
Fig. 3 Typical LIBS spectrum for the green house soil sample # 2
line intensity is plotted as a function of incident laser
energy. As clear form (Fig. 7), the LIBS signal is lin-
early dependent on the incident laser energy which is
indicated by the least square fit R2 = 0.999.
3.3. Calibration curves for quantitative analysis
of nutrients
A typical plot of the LIBS signal versus Ca and Zn con-
centrations for soils from the cultivated plots (Green
Fig. 4 Typical LIBS spectrum for the green house soil sample # 3
135
house soil sample 4) shows excellent correlation and
provides a calibration curve (Figs. 8A and 8B). Similar
calibration curves were drawn for all other important
nutrients present in the soil sample. The calibration
curves were applied for the prediction of the contents
of all nutrients present in the five samples from the
cultivated plots. The concentration of the detected nu-
trients is listed in Table 1 and the concentration of the
nutrients in different sample (1, 2, 3, and 5) is then
compared with Sample 4 which is taken as a standard
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136 Environ Monit Assess (2007) 124:131139

Fig. 5 Typical LIBS spectrum for the green house soil sample # 4

value. The % variation normalized to sample collected
from location 4 of the various nutrients is presented
in Table 2. It is worth mentioning that sample 4 has
the highest nutrient concentration. It is clear from the
Table 2 that LIBS technique is highly useful for the
prediction and measurements of nutrients contents at
various locations in the green house soil. It is rapid and
accurate technique for such applications.
3.4. Precision and accuracy of the LIBS method
The precision is defined as the repeatability of an an-
alyze measurements, usually determined as the rela-
tive standard deviation (RSD) as follow (Body and
Chadwick, 2001; Bolger, 2000)
RSD = standard deviation/mean (1)

Fig. 6 Typical LIBS spectrum for the green house soil sample # 5

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Environ Monit Assess (2007) 124:131139 137

Table 1 Concentration of different nutrients in the soil sample detected with LIBS and conventional ICP spectrometer in green house
soil sample-4

Sr. no. Element Wave Length (nm) Concentration LIBS (ppm) Concentration ICP (ppm)

1 Al 460.986 1630.5 1575

2 Ba 553.548 19.03 17.3
3 Ca 393.366 3830.1 35729
4 Cr 425.433 11.9 10.9
5 Cu 515.324 8.07 7.34
6 Fe 407.835 2670.8 2428
7 K 404.721 454.3 413
8 Mg 518.36 6694.7 6177
9 Mn 403.449 74.1 67.4
10 Na 588.995 740.1 681
11 Ni 313.41 10.98 9.99
12 P 255.325 1010.9 919
13 S 547.929 1310.9 1249
14 Si 250.69 1080.6 996
15 Sr 460.733 377.3 343
16 Ti 399.864 82.1 75.6
17 V 440.85 9.55 8.69
18 Zn 330.30 40.4 36.8

For green house samples the precision of LIBS mea- 4. Conclusions

surements depend on the complexity of the sample,
homogeneity of the sample, and the reproducibility of
the laser shots. Typical values obtained for our LIBS
setup are in the range 110%. In our case for green
house soil samples the precision was 2%.
The nutrient distribution and contents were measured
with Laser Induced Breakdown Spectroscopy for green
house samples collected from Tomato and Cucumber
cultivated fields. As complete understanding of the

Fig. 7 Dependence of Calcium - 393 nm line intensity for the soil sample # 4 on incident laser energy

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138 Environ Monit Assess (2007) 124:131139

Fig. 8 Calibration curves

for Potassium and Zinc

nutrient distribution and concentration assessment is a
critical part of growing proper crop in the farm, we iden-
tified and quantified nutrients in soil samples taken un-
der the same condition from different locations of green
house farm (Tables 12) and obtained the spectra for
these soil samples. The results showed excellent corre-
lation with the results obtained from ICP and the cali-
bration curves were effective in quantifying the nutrient
concentration. This study demonstrated that the LIBS
is an excellent tool for assessing nutrient distribution
in green house soil samples and such set up can differ-
entiate clearly the un even distribution of nutrients at
various location inside the same field. The distribution
scenario and mapping of the detected nutrients with this
technique could be useful for the grower in the proper
management of nutrient and to enhance the yield.

Table 2 Comparison of important nutrients and their percentages in green house soil samples (collected form different locations)
detected with our LIBS setup

Nutrient Wavelength (nm) Sample no. 1 (%) Sample no. 2 (%) Sample no. 3 (%) Sample no. 4 (%) Sample no. 5 (%)

Ca 393.366 50.9 28.09 11.6 100 22.7

Fe 526.95 82.4 16.48 27.1 100 36.63
K 404.721 93.3 60 26.6 100 50
Mg 518.2904 81.6 18.36 20.4 100 25.5
Mn 403.449 47.6 10.04 15.2 100 35.7
Na 588.995 69.07 18.55 26.3 100 31.25
Ni 313.41 56 18 20 100 25
P 255.325 71.4 17.85 11.9 100 50.5
S 547.929 47.6 10.04 15.23 100 35.7
Si 250.69 66.6 14.28 13.33 100 47.61

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Acknowledgements The support by the Physics Departments
and King Fahd University of Petroleum and Minerals is grate-
fully acknowledged. One of the author (T.H.) is thankful to Na-
tional University of Science and Technology and Government
of Pakistan for finacial support for his Ph.D work. He is also
thankful to KFUPM for its hospitality and permission to work at
its research facilties.
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