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Calibration Curve with Improved Limit of Detection for

Cadmium in Soil: An Approach to Minimize the Matrix
Effect in Laser-Induced Breakdown Spectroscopic
Analysis
a a b a c a
Shiwani Pandhija , Nilesh K. Rai , Ashok K. Pathak , Awadhesh K. Rai & A. K.
d
Choudhary
a
Laser Spectroscopy Research Laboratory, Department of Physics , University of Allahabad ,
Allahabad , India
b
Inorganic and Physical Chemistry , Indian Institute of Science (IISc) , Banglore , India
c
Department of Physics , Ewing Christian College , Allahabad , India
d
Institute Instrumentation Center , Indian Institute of Technology , Roorkee , India
Accepted author version posted online: 01 Aug 2013.Published online: 29 Apr 2014.

To cite this article: Shiwani Pandhija , Nilesh K. Rai , Ashok K. Pathak , Awadhesh K. Rai & A. K. Choudhary (2014) Calibration
Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced
Breakdown Spectroscopic Analysis, Spectroscopy Letters: An International Journal for Rapid Communication, 47:8, 579-589,
DOI: 10.1080/00387010.2013.828758

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 Spectroscopy Letters, 47:579–589, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0038-7010 print=1532-2289 online
DOI: 10.1080/00387010.2013.828758

Calibration Curve with Improved Limit

of Detection for Cadmium in Soil: An
Approach to Minimize the Matrix Effect in
Laser-Induced Breakdown Spectroscopic
Downloaded by [Memorial University of Newfoundland] at 12:17 18 July 2014

Analysis
Shiwani Pandhija1,
Nilesh K. Rai1,2, ABSTRACT The present article describes a working or combined
Ashok K. Pathak1,3, calibration curve in laser-induced breakdown spectroscopic analysis, which
Awadhesh K. Rai1, is the cumulative result of the calibration curves obtained from neutral and
and A. K. Choudhary4
1
singly ionized atomic emission spectral lines. This working calibration curve
Laser Spectroscopy Research
reduces the effect of change in matrix between different zone soils and cer-
Laboratory, Department of
tified soil samples because it includes both the species’ (neutral and singly
Physics, University of Allahabad,
Allahabad, India ionized) concentration of the element of interest. The limit of detection
2 using a working calibration curve is found better as compared to its constitu-
Inorganic and Physical
Chemistry, Indian Institute of ent calibration curves (i.e., individual calibration curves). The quantitative
Science (IISc), Banglore, India results obtained using the working calibration curve is in better agreement
3
Department of Physics, Ewing with the result of inductively coupled plasma–atomic emission spectroscopy
Christian College, Allahabad,
as compared to the result obtained using its constituent calibration curves.
India
4
Institute Instrumentation
KEYWORDS calibration curve, laser-induced breakdown spectroscopy (LIBS),
Center, Indian Institute of
Technology, Roorkee, India limit of detection, matrix effect, soil

Received 22 January 2013;
accepted 22 July 2013.
Address correspondence to
Awadhesh K. Rai, Laser Spectroscopy
Research Laboratory, Department of
Physics, University of Allahabad,
Allahabad-211002, India. E-mail:
awadheshkrai@rediffmail.com
Color versions of one or more of the
figures in the article can be found
online at www.tandfonline.com/lstl.
INTRODUCTION
It is known that when laser-induced plasma is under local thermal equi-
librium, the integrated intensity of the emission line of elemental species can
be expressed in terms of the atomic and thermodynamic properties, includ-
ing species concentration.[1] The concentration of any species present in the
target material can be determined by measuring the intensity of the atomic
lines of the species present in laser-induced breakdown spectroscopy (LIBS)
spectra of the target material. There are several ways to determine the
concentration (i.e., for the quantitative analysis); one of the most popular
methods is the calibration curve method.[2–9] In this method, a curve
between the integrated intensity of the atomic emission of the element
and the corresponding concentration of that element in the standard
579
 samples is drawn. The concentration of the element
in the unknown sample is determined by measuring
the intensity of the corresponding atomic emission in
the LIBS spectra of the sample and using the above
calibration curve. This procedure is most practical
for extracting quantitative information about the con-
stituents of the sample for which the standard or cer-
tified reference material (CRM) is easily available.
However, the laser–material interaction is highly
matrix dependent and therefore the analysis is based
on the assumption that the variations in the matrix
between the unknown and known must be mini-
mal,[1] which is not easy to maintain in the case of
environmental samples like soil. The mass ablation
rate depends on the nature of the matrix, which in
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turn compels matrix-matched standard samples to
be used for the calibration curve. But in some cases,
such as environmental, concrete, steel, glass sam-
ples, and so forth, the matrix of the sample to be ana-
lyzed is unknown, the certified reference materials
(CRMs) are not available, and calibration curves are
prepared using artificially prepared CRMs. In such
cases, there might be a difference in the excitation
conditions of CRM and the sample to be analyzed,
which leads to error in quantitative estimation.
Many research groups are currently working on
reducing or eliminating the effect of matrix on quan-
titative measurements. Aragon et al.[10] has proposed
a straightforward method to minimize the effect of
plasma state variations on quantitative measure-
ments. In the quantitative estimation of minor com-
ponents of steel samples, they used reference iron
lines having the same degree of ionization and an
upper energy close to the analytical lines. Another
analytical model, developed by Chaleard et al.,[11]
describes the line emission intensity as a function
of vaporized mass and the plasma excitation tem-
perature. The emission line intensity is normalized
with the acoustic signal intensity, which is pro-
portional to the vaporized mass, and the exponential
factor of excitation temperature. Panne et al.[12] have
proposed another normalization procedure using the
line intensity ratio, which includes the Saha and
Boltzmann relationships. Fichet et al.[13] defined the
normalized calibration function, which includes the
ratio of analyte line intensity to the background. A
different approach based on the analysis of single
shot spectra has been proposed by Xu et al.[14] in
order to overcome the problems related to signal
580
instabilities. Martin et al.[15] applied the approach of
principal component regression (PCR) for wood,
which provides a calibration model rather than a
single plot.
The motivation behind this work is to develop a
working calibration curve that minimizes the matrix
effect and provides a more accurate and precise
determination of heavy metal concentration in
environmental samples, which is a worldwide prob-
lem of great concern. The quantitative analysis using
the traditional calibration curve method is based on
the assumption that the distribution of elements
among the different excitation and ionization states
are the same for both the certified and unknown
samples. But the soil samples collected from different
areas have substantial differences in their matrices in
terms of structure, morphology, and so forth. In this
situation, the calibration curve obtained using a sin-
gle spectral line of an element present in certified
samples cannot precisely predict its concentration
in unknown soil samples. In this article, we have
developed a working calibration curve to reduce=
minimize the problem of the matrix effect, making
some modifications to the traditional calibration
curve approach. Thus, we have developed a work-
ing calibration curve that reduces the weak matrix
effect in the LIBS analysis. This working calibration
curve is used for the quantitative estimation of heavy
metal, Cd, in the soil near the Jajmau industrial area,
Kanpur, India.
EXPERIMENTAL SETUP
AND PROCEDURE
Apparatus
The schematic diagram of the experimental setup
applied for the analysis of the soil sample is
described elsewhere.[9] The LIBS experimental setup
consists of a Q-switched, Nd:YAG laser (Continuum,
USA Model No: Surelite III-10) spectrometer (Ocean
Optics, USA Model LIBS 2000þ) equipped with
a CCD detector, fiberoptic bundle, lens, translation
stage, and computer. Laser light having energy of
20 mJ=pulse is focused using a UV-grade fused silica
lens of 5 cm diameter and 15 cm focal length onto the
sample surface to produce a plasma. The light from
the micro-plasma is collected with a UV-grade fused
silica lens attached to the optical fiber tip, placed
S. Pandhija et al.
 approximately at a distance of 1.5 cm from the sam-
ple and at an angle of 45 degrees relative to the laser
beam. The collected light is then fed to a spec-
trometer and analyzed with the help of a PC using
LIBS software. Finally, the results of the quantitative
analysis are graphed and analyzed using ORIGIN
software.
Sample Collection and Preparation
The unknown soil samples were collected from
forming land near the industrial area of Kanpur city,
while the fresh soil sample was collected at a depth
of nearly 5 m of agricultural land, which is far away
from the industrial area. The collected soil is dried,
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ground to grain size (
mm), and sieved using a mesh
size of 100 mm. The sieved soil was spiked with
a solution of cadmium sulphate having known
concentrations of Cd. To make sure that the distri-
bution of solution is uniform throughout the sample,
the paste of the sieved soil sample was prepared with
cadmium sulphate solution and was kept at room
temperature for 7 days to get it dry. The dried soil
samples thus prepared were used to form the pellets
and are called reference=standard=known samples
having known concentration of Cd. The pellets were
formed by putting a pressure of 20 tons for 3 min in
a hydraulic machine. Before spiking, the LIBS spectra
of the fresh soil samples were recorded, which did
not show any spectral signature of Cd, and this
clearly demonstrates that the fresh soil is free from
Cd. The soil sample was placed on a rotational stage
to ensure that every laser shot is incident on a fresh
surface of the sample. Each spectrum is the
accumulation of 100 laser shots.
THEORETICAL MODEL
The variation in the composition of samples like
soil, sludge, steel, cement, and glass, which leads
to the variability in their surface absorption,
reflection, and thermal conductivity, affects the
laser–matter interaction.[5,16] A number of cases have
been reported in the literature for which the
traditional calibration curve method proved to be
unsuitable.[17] One example was shown by Eppler
et al.,[17] who investigated the effect of chemical spe-
ciation on analyte emission intensity in sand and soil
samples. The calibration curves were built using dif-
Improved Limit of Detection for Cadmium in Soil
ferent standard samples, prepared by doping with
the same element but in different chemical forms
(oxide, carbonate, sulfate, chloride, etc.), and had
different slopes. Therefore, it was concluded that
the accuracy of the measurement of the concen-
tration using the calibration curve is reduced when
the exact speciation of the target material is
unknown, which is most common while working
with the soil samples.
In the LIBS technique, the quantitative analysis
using the calibration curve method is based on the
following equation:
gk eEk =KB T
Ikki ¼ FCs Aki ð1Þ
Us ðT Þ
where the measured integral intensity Ikki corre-
sponds to the transition between the upper-level k
and the lower-level i, Aki is the transition probability
in sec1, gk is the degeneracy factor (dimensionless),
Cs is the concentration of the emitting atomic spe-
cies, Us(T) (dimensionless) is the partition function
of that species at plasma temperature T, kB is the
Boltzmann constant, Ek is the upper energy level, k
is the wavelength of the transition, and F is an
experimental parameter that takes into account the
optical efficiency of the collection system.
Under the calibration curve approach,[7] using Eq.
(1), a calibration curve is drawn between the spectral
line intensity of an atomic=elemental species (Ikki )
versus the concentration of that atom=element (C)
present in the sample (not species concentration,
Cs). The calibration curve correlates with the emission
intensity of the atomic spectral line of element
in plasma to the total element concentration in the
sample.[7] The concentration of the element in
the unknown sample can be obtained by measuring
the intensity of the above-selected line in the LIBS
spectra of the sample and observing the corresponding
concentration value from the calibration curve.[2,18]
The analysis using the calibration curve method is
absolutely correct when there is a consistent relation-
ship between elemental=species concentration in
standard as well as unknown samples and the species
concentration in their corresponding plasma. This
approximation can be considered satisfactory only if:
. Sample composition, morphology, and so forth
that are affecting the plasma characteristics are
581
 constant during recording the LIBS spectra of stan-
dard and unknown samples.
. The distribution of analyte element among the dif-
ferent excitation and ionization states remains the
same in laser-induced plasma of standard and
unknown samples.
This assumption fails when the chemical speciation
of matrix is different in the reference material and
unknown sample. Thus, there is an error associated
with the results of predicting the concentration of
an element in different area soil samples using the
calibration curve.
The working calibration curve has been
developed in order to increase the reliability of the
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traditional calibration curve method. This working
calibration curve, which includes the effect of distri-
bution of atomic population within the neutral and
ionized state, is modeled. In this working calibration
curve, a plot between intensity of one neutral atomic
line and one ionized atomic state line of an element
versus its concentration in the sample is drawn. As in
this model, the spectral lines corresponding to the
neutral atom and ionized state atom are introduced;
therefore, any variation in the distribution of atomic
population between the neutral atom and ionized
state atom in the laser-induced plasma of unknown
and standard samples does not introduce any error
in measurement of total concentration of an element
in the unknown sample using this working cali-
bration curve.
For drawing the calibration curve to evaluate the
concentration of elements in the unknown sample,
we assume that
II / CI / Concentration of element
or ð2Þ
III / CII / Concentration of element
where II and III are the intensity of spectral lines cor-
responding to neutral and singly ionized state atoms,
respectively; CI and CII are the concentrations of
atoms of the elements in the neutral state and singly
ionized state, respectively; and C (¼CI þ CII) is the
total concentration of that element in the sample.
Therefore, to generalize the use of the calibration
curve in all above said situations, like minor differ-
ences in the matrices of standard and unknown
582
samples, Eq. (2) may be written as:
II / CI ) II ¼ mI CI þ b ð3Þ
III / CII ) III ¼ mII CII þ b0 ð4Þ
II þ III / CIII ð5Þ
II þ III ¼ mIII CIII þ b00 ð6Þ
As CI, CII, and CIII reflect the same meaning (i.e.,
concentration) of element in target samples, Eqs.
(3), (4), and (6) will give similar information
(elemental concentration); but Eq. (6) is supposed
to give a more accurate result than that given by
Eqs. (3) and (4). This is because if there is any
change in laser matter interaction, the intensity of
the spectral line corresponding to the neutral atom
is reduced, and then the intensity of spectral lines
corresponding to the singly ionized atom may be
enhanced.[2] This is due to the decreased concen-
tration of the neutral atom and increased concen-
tration of the singly ionized state atom in the
laser-induced plasma,[2] but the total elemental con-
centration predicted by the new working calibration
curve remains unaffected.
RESULTS AND DISCUSSION
In India, a serious environmental disaster is
brewing in the villages of Jajmau at Kanpur (which
is one of our investigated sites) on account of the
supply of hazardous irrigation water to the farmlands
near it. The map of this contaminated site is shown
in Fig. 1. This heavily contaminated water, which is
being supplied to the fields for irrigation, has led to
serious environmental and public health concerns.
Here, we are emphasizing the detection of cadmium
because it is being recognized as one of the most
toxic heavy metals[19] that reaches vegetable crops
due to their contaminant growth media (soil, air,
nutrient solutions), from which these are taken up
by the roots or foliage. There a number of interlinked
concerns that have come: year after year destruction
of standing agricultural crops, ornamental plants,
and aquatic life in the river; contamination of food
chains, including milk and soil; and finally, a multi-
plicity of diseases hitting the villages.[20]
Therefore, it is essential to detect and quantify the
amount of Cd present in the soil of forming land near
S. Pandhija et al.
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FIGURE 1 Map of Kanpur district, indicating the Jajmau area from where the soil is collected.

the industries. Different steps are required to analyze de-excitation channels responsible for the different
the soil samples by the LIBS technique and are dis- emission lines of the cadmium is shown in Fig. 3(a)
cussed in the following sections. and 3(b).

LIBS Spectra of Cadmium Sulphate

The second harmonic, 532 nm, of the Nd:YAG
laser having a power density of 2.3  103 GW-
cm2 was focused on to the pellet of pure
cadmium sulfate (Merck Pvt. Ltd.) to produce
the laser-induced plasma. Figure 2 show the
LIBS spectrum of cadmium sulphate in the spectral
region 200–380 nm, which contains almost all
spectral lines of Cd II (singly ionized atom)
and a few prominent lines of Cd I (neutral atom).
The assignment of the Cd lines is straightforward
as the levels belonging to the lower and upper
state configurations are well known and tabulated FIGURE 2 LIBS spectra of pure Cd sulphate in the wavelength
in the NIST database. A schematic diagram of region 200–380 nm.

Improved Limit of Detection for Cadmium in Soil 583

Downloaded by [Memorial University of Newfoundland] at 12:17 18 July 2014
FIGURE 3 (a) Atomic energy level diagram of Cd I (neutral atom). (b) Atomic energy level diagram of Cd II (first ionization state atom).
LIBS Spectra of Standard Soil Samples
and Cd-Contaminated Soil Samples
The LIBS spectrum of Cd-doped reference soil
sample is shown in Fig. 4. The characteristic emission
lines (Table 1) of Be, C, Cu, K, Mg, Mn, Na, P, Sn, Sr,
V, W, Si, Al, Fe, Ti, Ca, and so forth are identified
using NIST data[21] and are tabulated in Table 1,
which clearly shows the presence of these elements
in the soil sample. Along with the above atomic
lines, the prominent atomic lines of Cd at 228.8 nm,
340.3 nm, 346.6 nm, 346.8 nm, 361.0 nm, 361.2 nm,
467.8 nm, 214.4 nm, 226.5 nm, 231.2 nm, 257.3 nm,
and 274.8 nm are also present in the soil sample.[21]
584
The contaminated soil samples are collected
from different parts of the Kanpur industrial area. The
LIBS spectra of Cd-contaminated soil samples are
obtained, and one of such spectra is shown in Fig. 5.
Calibration Curves
Calibration curves for quantitative analysis of
Cd in soil samples were prepared by measuring the
area of specific atomic lines present in the LIBS spec-
tra of standard soil samples using OOILIBS (2000þ)
software. Average spectra of 100 laser sparks formed
on the surface of each soil pellet containing a specific
impurity over the 20–1000-ppm concentration range
S. Pandhija et al.
Downloaded by [Memorial University of Newfoundland] at 12:17 18 July 2014
FIGURE 4 LIBS spectra of Cd-doped reference soil sample
in the spectral region 205–345 nm.
TABLE 1 Observed Wavelengths in the LIBS Spectra of the Soil
Observed wavelengths (nm) in LIBS
spectra
234.8, 313.0
247.8,229.6
230.7, 345.3
267.7, 283.5, 359.3, 425.4
217.8, 224.4, 324.7, 327.3
404.4, 404.7
277.9, 285.2, 382.9, 279.5
257.6, 259.3, 279.8,403.0, 403.3
330.2, 328.5
214.9, 253.3, 253.5, 255.3, 458.8,
460.2
270.6, 283.9, 303.4, 380.083, 386.3
407.7, 421.5, 460.7, 496.2
310.2, 311.0, 318.3, 411.1, 437.9,
438.4
203.0, 400.8, 407.4, 202.6
200.6, 206.2, 213.8, 250.2
272.1, 370.6, 373.6, 393.3, 396.8,
442.5
281.6, 308.2, 309.2, 394.4, 396.1,
466.3
205.8, 220.8, 221.0, 221.6, 250.6,
251.6, 288.1
365.3, 398.9, 399.8, 430.5, 498.1,
499.1, 334.9, 336.1
248.3, 248.8,374.5,238.2, 239.5, 259.9
228.8, 340.3, 346.6, 346.8, 361.0,
361.2, 467.8, 214.4, 226.5, 231.2,
257.3, 274.8
Improved Limit of Detection for Cadmium in Soil
FIGURE 5 LIBS spectra of contaminated ‘‘soil sample A’’ in
the spectral region 205–345 nm.
is obtained for this purpose, and three such
spectrums are used to get one data point (and corre-
Elements detected
sponding error bar) used in the calibration curves.
In the LIBS spectra of Cd (Fig. 2), we observe sev-
Beryllium (Be)
eral groups of spectral lines of Cd II (singly ionized)
Carbon (C)
Cobalt (Co) distributed in the different wavelength regions, along
Chromium (Cr) with a spectral line at 228.8 nm of Cd I (neutral atom)
Copper (Cu) having appreciable intensity. As the LIBS spectrum of
Potassium (K) the soil is very dense (Fig. 5), the line chosen for
Magnesium (Mg) drawing the calibration curve should be free from
Manganese (Mn)
interference of other lines. In the beginning, the cali-
Sodium (Na)
Phosphorus (P) bration curve is drawn between the concentration of
Cd in the soil samples and the intensity of the neutral
Tin (Sn) atom spectral line at 228.8 nm and is shown in Fig. 6.
Strontium (Sr) The transition levels of this line (228.8 nm) are
Vanadium (V) shown in Fig. 3(a). It is clear from Fig. 6 that the cali-
bration curve, obtained using the intensity of this
Tungsten (W)
Zinc (Zn) line (228.8 nm), is linear (regression coefficient,
Calcium (Ca) R2
0.98) having a standard deviation of 20%. A
relatively large standard deviation (20%) in this case
Aluminum (Al) is due to a slight change in the experimental para-
meters (laser power, lens-to-sample distance, matrix
Silicon (Si)
effect of the sample) during recording of the LIBS
Titanium (Ti) spectra of different standard samples.
To reduce the standard deviation and influence
Iron (Fe) of experimental parameters like laser power, sample-
Cadmium (Cd) to-lens distance, and the nature of the matrix
elements of different samples, one can use the ratio
calibration curve, that is, a calibration curve between
585
 FIGURE 6 Calibration curve using absolute intensity of analyte
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Cd I (neutral atom) line at 228.8 nm.
the concentration of Cd in the standard soil samples
and the intensity ratio of two atomic lines (intensity
of analyte (Cd) line=intensity of any reference line).
Therefore, the ratio calibration curve is drawn using
the intensity ratio of the Cd 228.8-nm line with the Si
reference line (Fig. 7), since silica has a prominent
and interference-free line at 221 nm and also the
upper energy level of this line is close to the upper
level of the Cd 228.8-nm atomic line.
In similar way, another calibration curve is
obtained using the atomic line belonging to the first
ionization state of Cd at 226.5 nm, and the ratio
calibration curve (Cd 226.5 nm with the Si reference
line) is shown in Fig. 8. It is clearly seen from Figs. 7
FIGURE 7 Calibration curveusing ratio of intensity of analyte
Cd I (neutral atom) line at 228.8 nm with the intensity of internal
reference Si line at 221.0 nm.
586
FIGURE 8 Calibration curve using ratio of intensity of analyte
Cd II (singly ionized) line at 226.5 nm with the intensity of the
internal reference atomic line of Si at 221.0 nm.
and 8 that the ratio calibration curve is a straight line
with a relatively low value of standard deviation.
To draw the working calibration curve, we have
chosen two atomic lines of Cd: one corresponding
to Cd neutral species and the other corresponding
to the Cd first ionization state. The following criterion
has to be fulfilled in the selection of these atomic
lines: both lines should lie nearly in the same spectral
region so that the effect of the spectral response of
CCD should be the same for both lines.
1. Both lines are interference free, and they should
be optically thin.
2. Their upper energy level should be as close
as possible.
For the present working calibration curve, two
atomic lines of Cd, one at 228.8 nm, which belongs
to neutral species, and another at 226.5 nm, which
belongs to a singly ionized stage of Cd, are chosen.
The area under the profile of both the spectral lines
present in LIBS spectra of the standard soil sample
having specific concentrations of Cd are calculated.
Ten such data from 10 LIBS spectra are averaged.
In the same way, other cumulative intensities are
obtained from the LIBS spectra of reference materials
having varying concentrations of Cd. A calibration
curve (Fig. 9) is obtained between the intensity of
the neutral atomic line plus the intensity of the singly
ionized state of Cd versus concentration of Cd
in standard soil samples. Finally, the ratio of the
S. Pandhija et al.

FIGURE 9 Working calibration curve using sum of absolute
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intensities of analyte lines (Cd I and Cd II) at 228.8 nm and
226.5 nm, respectively.
intensity of the neutral atomic line plus the intensity
of the singly ionized state with the intensity of the
reference line (Si line at 221.0 nm) is obtained to
get the ratio calibration curve (Fig. 10).
We have chosen the Si spectral line at the 221.0-nm
line as a reference as it is close to both the selected
lines of Cd and its upper energy level is also close
to the upper level of both the lines. Finally, the
ratio of LIBS intensity [fCd I (228.8 nm) þ Cd II
(226.5 nm)g= Si (221.0 nm)] is plotted as a function
of the Cd concentration in the reference soil sample
(shown in Fig. 10) and fitted with linear fit having
a regression coefficient, R2,
0.995.
FIGURE 10 Ratio working calibration curve using ratio of
intensity of analyte lines (Cd I plus Cd II) at 228.8 nm plus at
226.5 nm, respectively, with intensity of the internal reference
atomic line of the Si line at 221.0 nm.
Improved Limit of Detection for Cadmium in Soil
TABLE 2 Comparison of LOD for Cd in Soil Estimated Using
Different Calibration Curves
Calibration curves LIBS LOD (ppm)
Calibration curve for Cd I (228.8 nm) 0.9
Calibration curve for Cd II (226.5 nm) 0.2
Working calibration curve 0.16
Limit of Detection
The limit of detection (LOD) is defined as the low-
est concentration that can be detected, which stands
for the lowest concentration that can be determined
with the present experimental technique. LOD can
be estimated by using the equation given below:[2,17]
LOD ¼ 3 rB =m ð7Þ
where rB is the standard deviation of the back-
ground and m is the slope of the calibration curve.
The value of LODs for Cd calculated by using differ-
ent calibration curves is estimated and tabulated
in Table 2. The LOD using working calibration
curves is found better as compared to its constituent
calibration curves (i.e., individual calibration curves).
The reason may be better signal stability even if there
is a small change during laser matter interaction.
Analysis of Unknown Soil Samples
To check the sensitivity of different calibration
curves obtained in the previous section, the two soil
samples (sample A and sample B) from two different
areas of the industries of the Kanpur city are col-
lected and brought to the laboratory. The pellets of
these soil samples are prepared to determine the
Cd concentration in soil samples (sample A and sam-
ple B) by recording their LIBS spectra. A portion of
the LIBS spectra of one of the unknown soil samples
(sample A) is shown in Fig. 5. The intensities of
atomic lines of Cd at 226.5 nm and 228.8 nm and Si
at 221.0 nm present in the LIBS spectra of sample A
and sample B are measured, and the concentrations
of Cd in these samples are determined by using
the calibration curves drawn in the previous section.
The results obtained by the entire calibration curve
are tabulated in Table 3. To check the validity of
our result obtained by the calibration curve method,
both of the samples are analyzed using the ICP-AES
method, and these results are also tabulated in
587
 TABLE 3 Estimated Concentration of Cd in Two Industrial Area Soil Samples, Using Traditional Calibration Curve, the Ratio Working
Calibration Curve, and the ICP-AES Method
ICP Calibration curve for Cd I
Sample A 508 ppm 543  10 ppm
Sample B 5.32 ppm 11  1.3 ppm
Table 2. It is clear from the table that the results
obtained by the traditional calibration curve are not
as close as the results obtained by the working cali-
bration curve and ICP-AES method. The probable
reason is that the matrix of Cd in unknown and ref-
erence samples=standard samples is different. In soil,
Cd is bound with organic compounds, carbonates,
and oxides and found mainly in the form of cad-
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mium acetate (Cd(CH3COO)2), cadmium carbonate
(CdCO3), cadmium oxide, and cadmium chloride
(CdCl2), and a small fraction of it might be bound
in sulfate form. But in the present work, reference
material=standard soil samples are prepared by using
the Cd sulfate compound solution because Cd sul-
phate is totally dissolved in the water, whereas the
other Cd compounds require some additional chemi-
cals to be dissolved in water. Therefore, to avoid any
additional contamination in reference samples, we
have preferred the Cd sulfate solution.
The working calibration curve is free from the
matrix effect; therefore, the LOD as well as analytical
results obtained by the working calibration curve are
found better. Hence, we can say that our working
calibration curve is more suitable for the quantitative
determination of contaminants in environmental
samples as it reduces the influence of matrix in
which analyte elements are embedded on the inten-
sity of the LIBS signal.
The limit of detection of Cd in soil samples by
using the working calibration curve is 0.16 ppm,
and the safe limit of Cd in soil decided by the
Environmental Protection Agency (EPA) is 1 ppm;
therefore, this working calibration curve is well suit-
able for the determination of Cd concentrations in
the soil samples of any area.
CONCLUSION
This article describes the development of a work-
ing calibration curve that can be used for the quanti-
tative estimation of elements in unknown samples
having slight variation in the morphology with the
588
Calibration curve for Cd II Working calibration curve
480  14 ppm 494  5 ppm
1  0.6 ppm 3.3  0.4 ppm
standard samples. The developed working cali-
bration curve reduces the dependency of LIBS signal
intensity on the matrices in which the analyte ele-
ments are embedded. This is because this working
calibration curve is unaffected by the distribution of
atomic population within the neutral and ionized
state as, in the present calibration curve, the intensi-
ties of both lines (neutral and ionized state) are
included. The Cd concentrations in soil collected
from the industrial area of Kanpur city is estimated
by the present working calibration curve, which is
more than the standard EPA limit of Cd in soil
(1 ppm); therefore, it is an alarm of danger to the
people living around that area because this toxic
element can enter their food chain in significant
amounts and can affect their health.
FUNDING
Financial assistance from the BRNS, BARC, Mumbai
(no. 2009=37=30=BRNS=2063) is gratefully acknowl-
edged. Nilesh Kumar Rai and Ashok Kumar Pathak
acknowledge the UGC-Dr. D.S. Kothari postdoctoral
fellowship and Teacher Fellowship Award under the
FIP Scheme, respectively.
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