Spectrochimica Acta Part B 64 (2009) 1073–1078

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Spectrochimica Acta Part B

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s a b

Evaluation of laser induced breakdown spectroscopy for cadmium determination

in soils☆
Dario Santos Jr. a,⁎, Lidiane C. Nunes b,c, Lilian C. Trevizan b, Quienly Godoi b,c, Flavio O. Leme b,
Jez Willian B. Braga d, Francisco José Krug b
a
Universidade Federal de São Paulo — UNIFESP, Rua Prof. Artur Riedel 275, 09972-270, Diadema-SP, Brazil
b
Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, Av. Centenário 303, 13416-000, Piracicaba-SP, Brazil
c
Departamento de Química, Universidade Federal de São Carlos, Rod. Washington Luís, km 235, 13565-905, São Carlos-SP, Brazil
d
Instituto de Química, Universidade de Brasília, Campus Universitário Darcy Ribeiro, 70904-970, Brasília-DF, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Cadmium is known to be a toxic agent that accumulates in the living organisms and present high toxicity potential
Received 31 December 2008 over lifetime. Efforts towards the development of methods for microanalysis of environmental samples, including
Accepted 30 July 2009 the determination of this element by graphite furnace atomic absorption spectrometry (GFAAS), inductively
Available online 8 August 2009
coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma-mass spectrometry
(ICP-MS) techniques, have been increasing. Laser induced breakdown spectroscopy (LIBS) is an emerging
Keywords:
Laser induced breakdown spectroscopy
technique dedicated to microanalysis and there is a lack of information dealing with the determination of
LIBS cadmium. The aim of this work is to demonstrate the feasibility of LIBS for cadmium detection in soils. The
Cadmium experimental setup was designed using a laser Q-switched (Nd:YAG, 10 Hz, λ = 1064 nm) and the emission
Soil signals were collimated by lenses into an optical fiber coupled to a high-resolution intensified charge-
Sediment coupled device (ICCD)-echelle spectrometer. Samples were cryogenically ground and thereafter pelletized
before LIBS analysis. Best results were achieved by exploring a test portion (i.e. sampling spots) with larger
surface area, which contributes to diminish the uncertainty due to element specific microheterogeneity.
Calibration curves for cadmium determination were achieved using certified reference materials. The
metrological figures of merit indicate that LIBS can be recommended for screening of cadmium
contamination in soils.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction Direct solid analysis by laser induced breakdown spectroscopy

Cadmium is a toxic element that can enter in the organism via the
alimentary and/or respiratory tract, and the main non-occupational
sources of this metal are vegetables, drinking waters, and air [1]. Other
important toxic elements sources in the environment are the intense
industrial activities leading to a pronounced increase in the concentra-
tions of these elements in natural waters, soils, and plants [2–6].
Environmental interest in cadmium has centered mainly on properties
such as high toxicity and cumulative poison in humans and animals [7].
Consequently, efforts towards the development of more effective, faster,
precise, and accurate approaches for cadmium determination in several
materials have been increased.
☆ This paper was presented at the 5th International Conference on Laser-Induced
Breakdown Spectroscopy (LIBS 2008), held in Berlin, Adlershof, Germany, 22-26
September 2008, and is published in the special issue of Spectrochimica Acta Part B,
dedicated to that conference.
⁎ Corresponding author. Fax: +55 11 4043 6428.
E-mail address: dario.santos@unifesp.br (D. Santos).
(LIBS) is a promise alternative for determination of contaminants in
environmental samples. The potential for in-situ field analysis is the
great attractive of LIBS and portable instruments have been evaluated
for this type of application [8–15]. However, the main problem that
has been faced to employ this technique for environmental analysis is
the interferences caused by matrix effects [12,16,17].
Hilbk-Kortenbruck et al. [18] proposed a rapid in-situ LIBS method
for the determination of As, Cd, Cr, Cu, Ni, Pb, Tl and Zn in soils. They
combined LIBS with laser induced fluorescence (LIF) for improvement
of detection limits of Cd and Tl. In this case, the pulse of a second laser,
which was tuned to an optical transition wavelength of the analyte of
interest, was directed into the plasma plume generated by laser
induced breakdown. The calibration curve was prepared by the
suspension of a dried and homogenized standard soil with metal salt
solutions. Afterwards, the soil solution was dried and homogenized
again. Finally, the sample material was mixed with a small amount of
wax and pressed to form pellets. The fluorescence radiation induced
by the second laser pulse was then evaluated for chemical analysis.
Increase in linear response range and reduction of matrix effects were
also observed with the combination of LIF.

0584-8547/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2009.07.030
1074 D. Santos Jr. et al. / Spectrochimica Acta Part B 64 (2009) 1073–1078
The determination of Cr, Cu, Fe, Mn, Ni, Pb and Zn in pellets of soil and
sewage sludge samples using LIBS was evaluated by Capitelli et al. [19].
The results obtained by LIBS were partially in agreement with those
obtained by ICP OES, but the relative standard deviation (%RSD) of
measurements by LIBS were generally higher (except for Cr). Authors
attributed the differences between results to physical effects related to
sample matrix, such as thermal properties, pellet surface, and texture of
the sample. It was also observed that craters formed on the surface of
soil and sludge pellets were quite different in shape and dimension.
The aim of this work is to show preliminary results obtained for Cd
determination in soils by LIBS.
2. Experimental setup
2.1. LIBS instrumentation
A schematic diagram of the LIBS system is shown in Fig. 1. Exper-
iments were carried out employing a Q-switched Nd:YAG laser (Brilliant,
Quantel, France) operating at the fundamental wavelength
(λ= 1064 nm), generating 5 ns pulses of (365 ± 3) mJ, in a 6 mm
diameter beam with quality factor M2 smaller than 2, at 10 Hz repetition
rate. The lens-to-sample distance (LTSD) was adjusted to assure a high
signal-to-noise ratio and the lowest standard deviation of measurements
between successive sampling spots. Individual samples were placed in a
manually controlled two-axes translation stage that was moved in the
plane orthogonal to the laser propagation direction. To collect the plasma
emission, a telescope, composed of fused silica lenses, was assembled
and coupled to a 600 µm core spectrometer optical fiber. The telescope
collection angle with respect to the laser optical axis was 25 degrees.
A model ESA3000 spectrometer (LLA Instruments GmbH, Germany)
equipped with Echelle optics and focal length of 25 cm with numerical
aperture of 0.22, which provides a 24.5 × 24.5 mm2 flat image plane, was
employed. This system assemblage is a compromise that offers
maximum resolution in the wavelength range between 200 and
780 nm with resolving power ranging from 10.000 to 20.000. The linear
dispersion per pixel ranges from 5 pm at 200 nm to 19 pm at 780 nm. The
wavelength calibration was checked against Hg and Zn atomic lines from
electrodeless discharge lamps (EDL II System, Perkin Elmer, Germany).
The detector is an ICCD camera, comprised of a Kodak KAF 1001 CCD
array of 1024 × 1024 pixels full frame (24 × 24 µm2) and a microchannel
plate image intensifier of 25 mm diameter coupled to a UV-enhanced
photocathode. The image signals are digitalized in dynamic range of
16 bits and further processed by an industrial computer using resident
software. The features of using echelle spectrometers equipped with
ICCD for analysis by LIBS methods can be found elsewhere [20].
2.2. Certified reference materials
CRMs were ground and homogenized by using a cryogenic mill with
a laboratory self-container liquid nitrogen bath model MA-775
Fig. 1. Optical setup and schematic diagram of the LIBS system.
(Marconi, Brazil) during 2 min. The potentialities of using cryogenic
grinding in other analytical applications are described elsewhere [6].
Pellets were prepared in a Spex model 3624B X-Press by transferring 0.5
to 0.8 g of powdered material to a 15 mm die set and applying between 2
and 8.5 ton cm− 2. The pellets were approximately 3 mm thick and
15 mm diameter. Boric acid or Ultrabinder® (Spex, USA) were used as
binder agents for pellets preparation. At least 10 spectra of each sample
were collected in 10 different test portions of the pellet.
The following certified reference materials were used: Montana
Soil — NIST 2710, Buffalo River Sediment — NIST 2704, and New York/
New Jersey Waterway Sediment — NIST 1944, from National Institute
of Standards and Technology; Toronto Harbour Sediment — TH2 from
National Water Research Institute; Soil — GBW 07411 from National
Research Center for CRMs; Soil — CRM030-050 and CRM025-050 from
Resource Technology Corporation; and Sewage sludge amended soil —
BCR143R from Institute for Reference Materials and Measurements.
3. Results and discussion
3.1. Sample presentation
LIBS has been frequently pointed out as an alternative to spectro-
chemical analysis without sample preparation steps. This consider-
ation can generally be appropriate for analysis of homogeneous
samples by LIBS. However, by taking into account the inhomogeneous
character of environmental sample, several problems can be expected
for quantitative analysis of complex matrix like soils and sediments.
Initially, we tried to simulate a simple way for field analysis by just
transferring the soil samples directly to a polyethylene sample-holder
and applying pressure manually by using a spatula. Applying 50 mJ
laser pulses, focused at sample surface, powder material was ejected
from the sample-holder towards the plasma. Under this condition, the
%RSD of shot-to-shot measurements was generally in the range from
35 to 70%. Moreover, it was observed that the craters formed by laser
pulses and the amount of particles ejected were strongly dependent
on the soil type in terms of clay and sand composition.
Recently, Bousquet et al. [12] reported the development of a mobile
system based on laser induced breakdown spectroscopy dedicated to in-
situ analysis of polluted soils. The authors showed the effect of sample
density by analyzing the same soil sample by LIBS without any
preparation (i.e. as a raw powder) and as a pressed pellet. They pointed
out that the LIBS signals of the raw sample were always smaller than
those obtained from the corresponding pressed pellet. They explained
this effect due to the ablation efficiency that was better on a compact
sample than on a non-pressed powder. As it could be expected, they also
showed that the sample density was an important source of variation of
the LIBS signal. A coefficient of variation ranging from 10 to 25% was
observed in the LIBS signals resulting from the ablation of a typical soil
prepared as a pressed pellet. This parameter underwent a 40% variation
when the soil was analyzed without sample preparation [12]. According
 D. Santos Jr. et al. / Spectrochimica Acta Part B 64 (2009) 1073–1078 1075

to the author, this large variability is a drawback for the quantitative LIBS
analysis of soil samples, and obviously depends on the physical and
chemical properties of sample. The author also presented a nice
discussion concerning to the representativeness of the small amount
of matter analyzed by LIBS with respect to the whole soil sample
compared to other spectrochemical techniques [12].
In this way, the LIBS technique was initially evaluated as an
alternative for laboratory analysis by taking into account the sample
preparation steps for microanalysis. Samples were dried and, generally,
homogeneous particles size distributions with particles diameter lower
than 45 µm were obtained after grinding. Thereafter, samples were
prepared as pressed pellets by applying pressures ranging from 2 and
8 ton/cm2 for 2 to 10 min. The use of boric acid or Ultrabind® as binder
was also evaluated by homogenizing the binder and the sample amount
previously ground in a vortex mixing for 5 min. The results obtained
showed that, even for pellets preparation, the soil composition is
determinant and only for clay soil was possible to obtain consistent
pellets without binder. Pellets prepared from sand soils and boric acid
up to 25% m/m presented some crakes after laser pulses. Increasing the
concentration of boric acid up to 50% m/m, leads to diminishing the
analytical signal and increasing the %RSDs. In general, for all samples
analyzed, 2 ton/cm2 for 5 min were necessary for pellets preparation and
lower %RSD were obtained using Ultrabind® 10% m/m. In addition,
similar craters for different types of soil samples were observed after
laser ablation using binder. Most recently, Arroyo et al. [21] demon-
strated that it is possible to prepare soil pellets without binder by
reducing the particle size of the sample to less than 1 µm diameter for
further analysis by laser ablation-ICP-MS. In spite of the excellent results
obtained by this approach, it must be considered that in the LIBS method
proposed herein, the laser energy necessary to generate an analytical
signal is much higher when compared to LA-ICP-MS. In this way, most
pellets prepared from sand soils without binder were broken or cracked
after laser shots. Anyhow, future LIBS investigations can be addressed to
analyze soil pellets by following the procedure recommended by the
authors for pellet preparation [21].

3.2. Experimental condition

In LIBS analysis the laser fluence on the sample surface depends on
the lens-to-sample distance (LTSD) and affects the mass of ablated
material and the emission line intensities [13]. In general, the laser
energy is controlled to avoid the occurrence of plasma shielding effect
and the LTSD is maintained few millimeters shorter than the lens focal
length. As a consequence, most of the laser energy is deposited into
the material bulk and the spot diameter is in the order of few
micrometers, which is very useful for high spatial resolution surface
analysis. However, considering the inhomogeneous character of
powdered samples, the lens-to-sample distance can be adjusted for
different focusing condition and obtaining a higher spot area to assure
the lowest relative standard deviation of measurements between
successive sampling spots. In this work, the laser pulses were focused
on the sample pellet by a fused silica plano-convex lens (200 mm focal
length). We have investigated LTSD from 160 up to 200 mm with
different fluences in order to avoid plasma shielding effect at high
laser energies. As could be expected, better precision repeatability
was obtained by exploring a sampling spot with larger surface area,
which contributes to diminish the uncertainty due to element specific
microheterogeneity. The LTSD was kept at 165 mm and in this optical
arrangement the calculated beam radius at the sample surface was
525 µm, resulting in a maximum fluence and irradiance of 42 J cm− 2
and 8.109 W cm− 2, respectively, when operating at the maximum
laser pulse energy (i.e. 365 mJ). The craters diameter produced after
10 consecutive laser pulses on the pellet surface was generally in the
1.1–1.3 mm range for different laser fluence and sample types.
Fig. 2a and b show a typical temporal evolution of a fragment of
LIBS spectra from 1 to 5 µs delay time after the laser pulse and 5 µs
Fig. 2. Temporal evolution of the plasma spectrum induced in a soil pellet (CRM 020-050,
Cd 369 ± 46 µg/g). Integration time: 5 µs; signal data accumulated from 10 laser shots.
Fragments of spectrum showing the decay of lines (a) Cd II 214.441 nm, and (b) Cd II
226.502 nm and Cd I 228.802 nm.
integration time. Due to the transient nature of laser induced plasmas,
the population of the various species present in the plume rapidly
evolves with time. An intense contribution of the continuum to the
emission was observed when 1 µs delay time was employed. The
background emission decreased continuously when higher delay
times were used. After 2 µs the continuum emission rapidly decreases
as a consequence of the plasma expansion and cooling, and the ionic
lines become progressively narrower due to the decrease of the Stark
broadening effect [14]. After 3 µs the signal-to-background ratios
(SBR) did also decrease significantly. As a compromise to provide high
SBR for the selected wavelengths a 2 µs delay time was chosen for
further measurements.
The emission line intensities in LIBS depend on many factors,
including the ambient gas atmosphere [22]. It was observed that the
line emissions obtained under argon flowing at 0.5 L/min were at least
two-fold more intense than in the presence of air. This result is in
agreement with the effect of ambient gas on the LIBS plume observed
elsewhere [23–25]. In general, the presence of argon atmosphere
increases the plasma lifetime and analytical signal. This phenomenon
has been considered due to the smaller conductivity and specific heat
of argon gas with respect to the corresponding air values [24].
According to the authors such differences in the thermal properties
result in plasmas of higher temperature, leading to a stronger
emission, and also in a slower cooling of the plasma, thus implying
1076 D. Santos Jr. et al. / Spectrochimica Acta Part B 64 (2009) 1073–1078
a longer emission period [24]. In addition, the argon environment also
minimizes the formation of stable compounds such as oxides, which
would reduce the emissions of atomic and ionic lines. Wisbrun et al.
[25] pointed out that, in lower ionization potential atmosphere, the
plasma is easily produced and its final temperature is expected to be
higher. In addition, the cooling processes of the excited atoms in the
plasma are subjected to gas masses. When the surrounding
atmosphere is heavier, the collisional translational energy transfer is
less effective, and the plasma lifetime is longer. In general, the relative
line emission intensities are higher as the masses are heavier and
when the ionization potential is lower.
The excitation temperature of the plasma was estimated through
Boltzmann plots [13] using Fe(I) line emission from a plasma induced
in soil. At 2 µs delay time the spatially averaged value of the excitation
temperature at argon atmosphere was estimated as (9847 ± 255) K.
Although the temperature measurements analyzed by a Boltzmann
plot presented a low coefficient of variation, it should be mentioned
that the method is accompanied by errors related to the transition
probabilities [26].
As emphasized by Ctvrtnickova et al. [27], the knowledge of the
ablation/plasma threshold fluences is a good way to recognize the
amount of energy to start the material removal and control the ablation
process. The ablation threshold is the fluence level that causes an
irreversible damage of the sample surface whereas the plasma threshold
is the fluence level that generates a spectroscopic signal from the plasma
to be detected. Fluences under the ablation threshold does not produce
any relevant change in the sample surface while fluences much higher
than plasma threshold could lead to worse effects like plasma shielding
and self-absorption. The authors pointed out that the ablation and
plasma threshold fluences are characteristic for every material or even
for each sample form [27]. Consequently, the suitable laser fluence
should be investigated for each experimental case.
Fig. 3 shows the effect of fluence on cadmium line emissions. The
different fluences were obtained by controlling the laser energy and
maintaining the LTSD at 165 mm. The laser pulses were focused in the
pellet surface of soil with 10% m/m of Ultrabind®. A significant increase
in the cadmium emission net signals was obtained up to 23 and 28 J/cm2
for Cd I 228.802 nm and Cd II 226.502 nm lines, respectively. For Cd II
214.441 nm line, it was observed a significant increase in the signal
intensity up to 42 J/cm2. For fluences lower than 5.7 J/cm2 the signal
intensity was very low and sometimes was impossible to distinguish
any difference between analytical signal and noise. By applying fluences
of 2.8 J/cm2 it was possible to identify damages at the pellet surface, but
at this condition only high concentrations of cadmium (N350 µg/g) can
Fig. 3. Effect of fluence on the cadmium line emissions. Integration time: 5 µs; signal
data accumulated from 10 laser shots. (▲) Cd II 214.441 nm, (●) Cd II 226.502 nm, and
(■) Cd I 228.802 nm.
be detected by single-pulse method. The analyte emission fluence
threshold depends on analyte concentration. It should be commented
that observing the pellets in an optical microscope there was no
evidence of significant increasing in the crater depth for fluences higher
than 28 J/cm2 and only a minimal lateral damage was observed at higher
fluences. This effect can suggest that there was no increasing on the
ablation rate, probably due to partial plasma shielding effect. The signal
intensities would probably continue growing due to the plasma re-
excitation by enhanced energy. In addition, better sensitivity and better
correlations in calibration curves with CRMs were obtained by using
higher fluences. It is advisable to investigate if higher fluences could
diminish matrix effects on particle decomposition and in analyte
desorption/excitation in different soils after ablation.
3.3. Analysis of samples
Pellets produced from certified reference materials were analyzed by
the described LIBS system herein by applying 10 consecutive laser shots in
10 different areas at the sample surface under argon atmosphere (0.5 L/
min). The results obtained demonstrated that there is the possibility of
spectral interferences of Fe I 214.519 nm, Ni II 226.446 nm, and As I
228.812 nm on the emission lines Cd II 214.441 nm, Cd II 226.502 nm, and
Cd I 228.802 nm, respectively. For cadmium determination using the Cd II
214.441 nm line a possible interference from Fe I 214.519 nm can occur if
lower spectral resolution is used (Fig. 4a). By using Cd II 226.502 nm line
the spectral interference of Ni II 226.446 nm was solved by using the peak
height or delimited area of cadmium signal obtained in ESA3000
spectrometer (Fig. 4b). The deconvolution of signal showed that the
interference of Ni at this concentration (i.e. 24.2±2.1 mg/kg) can be
neglected by using the peak height or integrating the peak area above
Fig. 4. Signal profile for cadmium lines at (a) 214.441 nm in SRM 2704 (Cd: 3.45 ± 0.22 mg/
kg; Fe: 41,100±1000 mg/kg) and (b) 226.502 nm in GBW 07411 (Cd: 28.2±1.3 mg/kg;
Ni: 24.2±2.1 mg/kg).
 D. Santos Jr. et al. / Spectrochimica Acta Part B 64 (2009) 1073–1078
226.500 nm. For higher Ni concentration the effect of interference should
be better evaluated. For cadmium determination using Cd I 228.802 nm
line it was observed interference from As I 228.812 when the soil
presented high concentration of arsenic, as showed in the Fig. 5c (i.e. SRM
2710, As: 626±38 mg/kg).
Fig. 5. Calibration curves for cadmium emission lines using certified reference materials.
Integration time: 5 µs; delay time: 2 µs; signal data accumulated from 10 laser shots.
Mass fractions in mg/kg: SRM 2704: 3.45 ± 0.22; TH2: 5.22 ± 0.46; SRM 1944: 8.8 ± 1.4;
SRM 2710: 21.8 ± 0.2; GBW07411: 28.2 ± 1.3; CRM 030-050: 58.4 ± 5.89 and BCR 143R:
71.8 ± 1.2.
1077
Fig. 5a–c show the calibration curves for cadmium achieved using
CRMs. Although most certified values are generally based on a
minimum sample mass from 150 to 250 mg, it was observed that they
can be used for analytical calibration purposes after homogenization.
The calculated coefficient of variation of the line intensities observed
in the plasma induced in each pellet of CRMs generally was lower than
20% (n = 10) and the uncertainty due to laser energy variation was
lower than 5%. The horizontal bars in the X-values indicate the
uncertainties of the certified mass fractions (at 95% confidence level).
Initially, it can be suggested that the main reason for the relatively
high coefficients of variation of the results is the microheterogeneity
of the analytes in the original sample. In this sense, it must be
observed that the uncertainties associated with the certified mass
fractions of reference materials used in this work are in the range from
1 to 16% at a 95% confidence level for test portions generally higher
than 150 mg.
The cadmium detection limits were estimated from certified
reference materials with the lowest mass fraction of the analyte in the
calibration curve. The estimated standard deviation of the background
(s), measured in the surroundings of the selected emission line, was
used (n = 10) and detection limits were calculated as 3s/b, where b is
the angular coefficient of the calibration curve. The calculated
detection limits were 1.3, 3.6, and 4. 0 µg/g for Cd II 214.441 nm, Cd
II 226.502 nm, and Cd I 228.802 nm, respectively. It is important to
note that at 214.441 nm a selective and intense line was observed,
leading to a more appropriate limit of detection. In the case of 226.502
and 228.802 nm lines and in the presence of spectral interferences a
multivariate model can be used to verify further improvements in the
above mentioned limits of detection.
The establishment of threshold values for cadmium concentration in
soils is difficult since the toxicity and bioavailability of cadmium is not
only dependent on the total content in soils but in other environmental
variables. In general, the recommended values for soil quality criteria are
between 1 and 3 mg/kg Cd, but these values depend on the soil
application and specific country legislation. In the Soil Guideline Values
for São Paulo State in Brazil, soil is considered contaminated when the
cadmium concentration is higher than the 3, 8, and 20 mg/kg for
agricultural, residential, and industrial soil, respectively.
4. Conclusion
In principle, the results demonstrate that LIBS can be considered as
an alternative technique for quantitative determination of cadmium
in soil. The limits of detection are appropriate for discrimination of
contaminated areas. The metrological figures of merit indicate that
LIBS fits for the purpose of cadmium determination, but there is a
need for development of CRMs with adequate homogeneity for
analytical calibration. In this aspect, the representativeness of the
analyzed sample is not only a problem for LIBS but also for other
techniques dedicated to microanalysis. Method validation is under
evaluation in our laboratory for a variety of soils and sediments. In
general, LIBS presented good results towards direct microanalysis and
clean chemistry. The main difficulty for LIBS analysis is the sample
presentation. The physical effects of matrix were diminished when
the samples were analyzed in pellets form. In this way, the proposed
procedure for sample preparation requires a grinding step, homog-
enization with a suitable binder and press for 5 min.
Acknowledgments
The authors are thankful to Fundação de Amparo à Pesquisa do
Estado de São Paulo (FAPESP, processes: 04/15965-2, 05/50773-0, 06/
06466-8, 07/01052-3) and to Conselho Nacional de Desenvolvimento
Científico e Tecnológico (CNPq, processes: 477385/2006-0, 301285/
2006-3) for financial support.
1078 D. Santos Jr. et al. / Spectrochimica Acta Part B 64 (2009) 1073–1078
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