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Phosphorus quantification in fertilizers using laser

induced breakdown spectroscopy (LIBS): a
Cite this: DOI: 10.1039/c5ay01615k
methodology of analysis to correct physical matrix
effects
Bruno S. Marangoni,*a Kleydson S. G. Silva,b Gustavo Nicolodelli,b Giorgio S. Senesi,c
Jader S. Cabral,d Paulino R. Villas-Boas,b Caroline S. Silva,e P. C. Teixeira,f
Ana Rita A. Nogueira,e Vinicius M. Benitesf and Débora M. B. P. Milorib

Received 23rd June 2015
Accepted 4th September 2015
DOI: 10.1039/c5ay01615k
www.rsc.org/methods
The aim of this study was to develop a quantitative method to determine phosphorus in fertilizers of
different matrix compositions using the laser induced breakdown spectroscopy (LIBS) technique. The
LIBS spectra were acquired on 26 samples of organic and inorganic fertilizers by using a low cost,
portable, gated CCD system in the atmospheric environment. Inductively coupled plasma optical
emission spectroscopy (ICP-OES) was used as the reference technique. A method was developed to
remove the outlier spectra and perform the baseline correction and peak normalization. By applying the
proposed corrections, the linear correlation between LIBS and ICP increased from R ¼ 0.76 to R ¼ 0.95.
An average error of 15% found in cross-validation of LIBS quantification appeared feasible for P
quantification in fertilizers. Two reference samples with different matrix compositions were also
analyzed, and the absolute error in the quantification was below 5%. Further, no significant fluctuation
was found in P quantification when LIBS was performed over 150 days.

mixtures of organic and mineral sources of P is now available on

1 Introduction
The increase of worldwide population poses a great challenge to
agriculture thereby requiring a considerable productivity
enhancement in the next few years. The development of new
techniques to monitor the amount of nutrients in soils and
fertilizers in a rapid and non-expensive way appears to be urgent
to optimize the application of fertilizers. Further, this moni-
toring will allow the regulatory agencies to optimize the fertil-
izer quality control and avoid fraud.
Phosphorus (P) is one of the most important nutrients for
agriculture, mainly in tropical soils. World reserves of phos-
phates are limited and concentrated in few countries. The
exploration of these reserves has become critical and the
average P concentration in industrial rocks has decreased
during the last few decades.1 The use of secondary P is
becoming an important strategy to save limited primary P
reserves.2 New fertilizers based on organic residues and
a
Departamento de Fı́sica, Universidade Federal de São Carlos, P.O. Box 676,
13565-905, São Carlos, SP, Brazil. E-mail: marangoni@df.ufscar.br
b
Embrapa Instrumentação, P.O. Box 741, 13560-970, São Carlos, SP, Brazil
c
Institute of Inorganic Methodologies and Plasmas-CNR-Bari, 70126 Bari, Italy
d
Instituto de Fı́sica, Universidade Federal de Uberlândia, P.O. Box 593, 38400-902
Uberlândia, MG, Brazil
e
Embrapa Pecuária Sudeste, P.O. Box 339, 13560-970, São Carlos, SP, Brazil
f
Embrapa Solos, Rua Jardim Botânico 1024, 22460-000, Rio de Janeiro, RJ, Brazil
the market. The use and commercialization of organic mineral
fertilizers in Brazil have increased in a rapid manner during the
last decade. Methods to check the nutrient content of these
fertilizers considering the possible effect of organic matter
interference are urgent and necessary.
As inorganic P fertilizers are usually extracted from rocks of
various compositions, the P composition indicated on fertilizer
packages may not be very accurate. The organic fertilizers are
even less monitored, and because it is extracted from organic
residues, their concentration variability is even higher. Thus,
the development of a method that can monitor the amount of
P in organic and inorganic fertilizers in a precise, rapid and
non-expensive way may result in a great environmental and
economic impact.
Over the recent years, the laser induced breakdown spec-
troscopy (LIBS) technique has been applied in several elds3
including soil and fertilizer analysis.4–7 The main advantage of
LIBS is the capability to obtain rapid and relatively non expen-
sive measurements with minimum sample preparation.8,9 The
concentration of an element can be determined using a cali-
bration curve or by multivariate methods,10 both of which
require a reference technique. Once the model is developed and
tested, LIBS can be used as a rapid analytical technique that
does not require a huge computer capability. Another meth-
odology to determine the sample elemental concentration by

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LIBS uses the calibration free technique5 that requires a
detailed analysis of spectra and extended data processing. This
method is commonly used for simple matrix samples in a semi
quantitative approach. Further, portable LIBS equipment have
been developed allowing rapid in situ measurements.
In particular, in the last decade LIBS methods were devel-
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oped and applied successfully for real-time, on-site, on-line
automated quantitative analysis of P and other relevant
elements, including Si, Ca, Mg, Al, and K, in phosphate ores and
potassium fertilizers.11–13 An acceptable level of precision and
accuracy was achieved with 2–4% relative standard deviations
for most elements,11 and the comparison of LIBS on-line data
with control chemical analysis revealed good correlations.12,13
Further, real-time LIBS data of the P/Si ratio provided a simple
and reliable indicator of phosphate ore rock quality.14 However,
the elemental determination in fertilizers has involved samples
with similar matrix compositions and no LIBS application has
been performed on organic fertilizers.
The main goal of this study was to develop a LIBS analytical
methodology for P quantication in organic and inorganic
fertilizer samples by using equipment featuring a spectral and
temporal resolution compatible with commercial portable LIBS
systems for in situ measurements.
2 Materials and methods
2.1 Samples
Twenty six fertilizer samples were used in this experiment: 5
phosphate rocks (PR) (Bayovar, Arraias, Gafsa, Arad and Djabel);
3 mineral fertilizers (monoammonium phosphate (MAP), single
superphosphate (SSP) and triple superphosphate (TSP)) and
18 organic mineral granulated fertilizers. The organic fertil-
izers were produced in laboratory scale especially for this
experiment. All samples were granulated and have variable
compositions (e.g. different sources of organic matter, P
content, and additives such as bentonite and silicates) to
create a contrasting range of characteristics normally found
in commercial products.
The organic fertilizers were mixtures of 60% poultry litter, in
natura or composted, and 40% commercial mineral fertilizers.
The samples consisted of spherical structures of approximately
2 mm diameter. To ensure homogeneity, samples were ground
and sieved through a 100 mesh sieve. For LIBS analyses, two
pellets of each sample were prepared by applying a pressure of 6
 108 N m2 for 30 s.
2.2 LIBS setup
The LIBS spectra were obtained using a LIBS 2500 spectrometer
(Ocean Optics, Dunedin, USA) equipped with a Q-switched 1064
nm Nd:YAG laser manufactured by Quantel (Big Sky Laser
Ultra50) with a maximum energy of 60 mJ per pulse and a
repetition rate of 10 Hz. The laser spot diameter on the sample
inside the ablation chamber was estimated to be around 100
mm. The plasma emission was collected by using a ber optic
bundle and addressed to seven spectrometers, each of which
consisted of a 2048 pixel CCD array. The experiments were
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conducted in air at atmospheric ambient pressure. The distance
between the sample and the optical ber bundle was approxi-
mately 7 mm. The spectra ranged from 189 to 966 nm with an
optical resolution of 0.1 nm.
For each pellet, 100 spectra (50 for surface side) were
obtained at different positions of the sample. Each spectrum
was the result of two accumulated laser shots, preceded by one
for cleaning. The LIBS equipment was operated with a laser
pulse of 8 ns and 60 mJ with an integration time of 2.1 ms for all
measurements. The optimized delay time for P line emission
was 2.5 ms.
2.3 LIBS data processing: baseline correction and spectral
normalization
The baseline correction for LIBS spectra was performed in two
steps. The rst step consisted of subtracting an electronic offset
from the spectra. In this case, a spectrum was obtained without
a sample and laser light. The measured spectrum was then
subtracted from the upcoming acquired spectrum. This proce-
dure was necessary because the spectrometer offset changed
daily. The second step consisted of correcting the added offset
in the spectrum for continuum plasma emission. To do this, a
line was drawn under the atomic emission peak passing
through four or ve not interfered points on each side of the
peak. If there were no points available around the emission
peak, because of the presence of other peaks, the region was
broadened until a clear region was found. A linear function was
then tted (Fig. 1a), and subtracted point by point from the
spectrum. The processed peak transition is shown in Fig. 1b.
Aer the spectral correction, a Lorentzian function was tted
to the peak prole in order to obtain the area of the emission
peak (A1). The same region selected to perform the Lorentzian
t was selected to limit the linear correction function (full line
in Fig. 1b), and the area under this line was also calculated (A2).
This latter value was then used to normalize the emission line
area (Af ¼ A1/A2). The nal area value, Af, was then correlated
with the reference technique measurements.
2.4 Reference technique
Inductively coupled plasma optical emission spectrometry (ICP-
OES) with a radial view conguration, model OPTIMA 3000
(Perkin-Elmer), was used as a reference technique for P quan-
tication. The ICP-OES measurements were performed on
solutions obtained by digestion of 1 g of each fertilizer sample
in 20 mL of nitric acid and 5 mL of chloridric acid at boiling
temperature.
2.5 Correlation analysis and line emission choice
The approach used for the rst analytical step, i.e. the choice of
an appropriate emission line for P, was to calculate the linear
Pearson's correlation (R) between each spectral point and the P
concentration measured by ICP-OES. Outliers spectra were
previously excluded using the spectral distance technique,15
named spectral angle mapper (SAM). This method allows
comparing two spectra and, based on their similarity, returns a
scalar value between 1 and 1. By imposing a limit to this
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Fig. 2 Correlation graph for P. The correlation was calculated

between the P concentration in each sample and the intensity points at
a fixed wavelength.

Fig. 1 Spectral region of a MAP sample where a linear function
(dashed line) was traced through the selected points (black dark dots).
Peak 1 used to determine the area of peak (A1) and that below it (A2).
nm; Fe II, 213.59 nm; Fe II, 213.60 nm and Fe II, 213.65 nm; and
Cu II, 213.60 nm. Thus, these transitions may overlap each other
and disturb the P emission line. To verify that these lines do not
interfere with the P line, a correlation analysis similar to the one
performed for P (Fig. 2) was performed for Fe and Cu concen-
trations measured by ICP-OES. The correlations with Fe and Cu
concentration in the region 213–216 nm were small (R around
0.25), thus Fe and Cu interferents were ignored. The elements
Al, Cr, K, Mg, Na, Ni and Zn were also analyzed and no signif-
icant interference was found. Thus the P line intensity at 213.62
nm is minimally interfered by others elements, and its intensity
is assumed to be almost exclusively due to the P transition.

number, we can exclude the spectra that are not similar to

the others.4 The percentage of the excluded spectra was about 3 Results and discussion
2–3%. A specic point of each averaged spectrum (points
having the same wavelength) was selected for each sample, Fig. 3 shows the average values of the P emission line areas
thus totaling 26 intensities. Then, a linear correlation between obtained by using the LIBS technique versus the P concentration
the peak intensity and the corresponding P concentration is obtained by ICP-OES. A linear t was performed in order to
performed. If the intensity at this point of the spectrum varied obtain a calibration curve model. The correlation found was R ¼
according to the P concentration, a correlation close to 1 (R
range from 1 to 1) was obtained. This procedure was repeated
for each spectral point, thus enabling us to draw a correlation
graph for P (Fig. 2), which indicated the spectral intensity
variation as a function of the P concentration. This pre-analysis
allowed speeding up the line emission identication process
and making the process more reliable.
The wavelengths indicated in Fig. 2 in the region 213–216
nm showed the highest correlation values for the entire spec-
trum (180 nm to 990 nm). Using the NIST database,16 and
considering the spectrometer precision (0.05 nm), these peaks
were referred to P atomic emission lines at 213.62 nm, 214.91
and 215.41 nm. The line at 213.62 nm was chosen for the cali-
bration model because it showed a little higher correlation than
the other two peaks, featured no apparent interference and
resulted in the higher peak intensity among these three peaks.
According to the NIST database,16 in addition to P transi-
tions, this region can also include the transitions of Fe II, 213.56 Fig. 3 Calibration curve for P in fertilizers samples.

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0.95, which is very satisfactory given the different compositions
of samples. The same calibration curve obtained without
applying the peak normalization procedure resulted in a
correlation of R ¼ 0.76.
Fig. 4 shows the cross-validation data. In this kind of vali-
dation, one sample is withdrawn from the 26 samples and it is
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not used to calibrate the model. The extracted sample is then
tested with the model. This process is repeated for testing all the
26 samples. In an ideal situation, all points in Fig. 4 would be
aligned perfectly with the dashed line, indicating a total
agreement between ICP and LIBS data. In the experimental
case, the point displacement is proportional to the quantica-
tion error (root mean square error) that resulted in 15% aver-
aged for all the 26 samples. The limit of detection (LOD) for P
quantication was 0.5%, which is acceptable for P quantica-
tion in fertilizers of different types of matrix compositions by
using portable LIBS systems. The LOD was calculated with the
equation LOD ¼ 3s/m, where s is the standard deviation of the
background signal and m is the slope of the calibration curve
referred to the P element analyzed.
Although, the average concentrations of Cu and Fe in our
samples are about 46 mg kg1 and 7500 mg kg1, respectively,
the quantication error does not change for samples. This
result conrms the previous observation that Cu and Fe do not
interfere with the P transition considered (213.62 nm) at the
concentration limit of the experimental system used, which
might not be the case for a more sensitive system. Further, the
lack of interference with the P emission line may also be due to
the high concentrations of P (more than 2.5%) in the fertilizers
examined.
In order to test the robustness of the calibration curve, two
reference materials were used: the fertilizer 695 CRM and the
phosphate rock 694 CRM. The reference values for P concen-
trations were 7.2% and 13.2%, respectively. The values
measured by LIBS were 7.4  0.9% for the fertilizer and 13.9 
2.2% for the rock. Thus, a good agreement was obtained with
the reference values within the measurement error.
Fig. 4 Cross validation data.
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In order to evaluate the possible variation of experimental
parameters over time, the P concentration in the phosphate
rock 694 CRM reference was measured by LIBS over almost half
a year. The quantication was performed using the same cali-
bration model developed for the 26 samples. The graph in Fig. 5
shows the evolution over time of the LIBS P value.
Fig. 5 shows that the measured P concentration remained
almost stable over time with a small and acceptable uctuation,
although the electronic background baseline (when no light is
being captured by the ber) varied considerably between
different days of measurements. To overcome this issue, a blank
spectrum (without sample) was acquired at the beginning of
each day in order to correct the spectral offset. Although most
LIBS systems can eliminate the electronic offset automatically,
in our system the automatic correction implied a small error,
thus the offset was removed manually as described in the
previous section. Despite the fact that the experimental system
was susceptible to some uctuations in that period of time, as
laser power uctuation (10%) and offset, the analysis based on
the area normalization was able to overcome such problems.
Thus, the system could easily handle some small perturbation,
which is very useful for portable LIBS systems that imply
handling with some perturbation due to transportation and
different environments.
The robustness of the quantication obtained relies mainly
on the proportionality of area A2 to the amount of ablated
matter in the plasma. The methodology applied is able to
overcome small uctuations in laser power, which interferes
directly with the amount of ablated material. Other authors
have used a normalization procedure similar to that used in this
work to prevent uctuations.17,18 Further, the normalization
applied was able to overcome the matrix effects of the different
kinds of fertilizers. This result would suggest that matrix effects
were mostly of physical and not chemical nature.19–21 Indeed, in
the case of physical matrix effects, the interaction between light
and matter affects mainly the amount of matter ablated from
different samples and does not affect the stoichiometry.
Fig. 5 LIBS P value evolution in the phosphate rock 694 CRM refer-
ence sample. The day zero corresponds to the same day in which the
calibration curve was built. The error bars represent the standard
deviation of a set of measurements.
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4 Conclusions
The applicability of the LIBS technique to the quantication of
elemental P in fertilizers of different compositions was studied.
A procedure was used to exclude the outliers, remove the offset
and obtain peak normalization. The nal average error in P
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quantication was 15%, which is acceptable for in situ
measurements and can be implemented in a portable system.
The study has considered a number of fertilizers of matrix
composition by applying a normalization correction to improve
the results.
The P concentrations in two reference samples with different
matrix compositions (a phosphate rock and a phosphate
fertilizer) were determined successfully by using LIBS. No
signicant uctuations were found in P quantication over time
for more than 150 days performed on a reference material. A
method was developed to correct the physical matrix effects for
different samples.
The LIBS technique was shown to apply well for high P
concentration fertilizers encompassing a wide range of
commercial fertilizers found in Brazil. For other materials with
low P contents (e.g. soils and minerals) further studies need to
be performed. Further possible applications of the LIBS tech-
nique will be directed to the analysis of other macronutrients in
fertilizers, such as N and K.
Acknowledgements
The authors thank FAPESP (2013/02165-7), CNPq, and
EMBRAPA for their nancial support of this study.
Notes and references
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