On the Selection of Variables for Quantitative Multi-

Elemental LIBS Using Artificial Neural Networks

a b a
Danny Luarte , Jorge Yáñez and Daniel Sbarbaro
a
Department of Electrical Engineering, University of Concepción, Concepción, Chile
b
Department of Analytical Chemistry, University of Concepción, Concepción, Chile
dannyluarte@udec.cl, jyanez@udec.cl, dsbarbar@udec.cl

1. Introduction
• The use of LIBS and Artificial Neural Networks for qualitative elemental analysis of mineralized rocks and soils has demonstrated to be a very
effective tool to deal with many practical issues such as interference and matrix effects.
• LIBS spectrum is a high dimensional signal. Each input of the ANN is associated to a given wavelength of the spectra. Thus, using the raw
spectrum as input of an ANN can lead to a model with serious overfitting problems.

• This work explores three approaches to reduce the dimension of the ANN’s input designed to quantify seven components from LIBS spectra.

2. Materials and Methods 4. Results and Discussion

• A three-layer ANN was implemented.
The input layer receives LIBS intensities
of certain spectral lines. The hidden layer
is optimized during the training step. The
output layer has many outputs as to the
number of components to be quantified.
• The calibration and validation data con-
sidered LIBS spectra of 6 certified pow-
ders and 25 rock samples [1].
• The ANN neural network was trained us-
ing Levenberger-Marquant with Bayesian
regularization. The number of hidden
neurons was set to 10.
• The KBest algorithm was implemented
with Python’s scikit-learn library.
3. Variable Selection Algorithms
• Prior knowledge. One reference line
per detectable element is selected. The
selection criteria were the strongest line
with no overlapping with other atomic
lines and no significant self-absorption [1].
• Principal component Analysis. It is
a lineal dimensional reduction technique
that transforms the input space into a
smaller dimension space [2]. The selection
of lines is based on the strongest lines as-
sociated with the most important loading
vectors.
• Univariate selection. Lines are found
by statistical inference methods selecting
the strongest relationship with the output
variable [3]. The test statistics normally
used are the χ2 test and F -test. This is
a univariate algorithm and therefore must
be applied separately for each element.
The use of prior knowledge (P.K.),
following the criteria described in Sec-
tion 3, leads to seven wavelengths; i.e.
one wavelength for each element [1].
Figure 1 (a) shows the validation re-
sults.
The loading vectors associated to
PCA of the training dataset are con-
sidered. The strongest lines associ- (a)
ated to the most important loading
vector were used as inputs to the
ANN. The total number of lines were
25. Figure 1 (b) shows the validation
results.
The F -test was applied separately for
each element. Thus, for each element,
the line with the highest score, based
on a F -test, was selected, giving a
total of 7 wavelengths. Figure 1 (c)
shows the validation results.
(b)
All the algorithms performed well
with and R2 bigger than 0.9, as seen
in Table 1. The best performing algo-
rithm was Kbest (R2 0.937) followed
by prior knowledge (R2 0.933) and
PCA based (R2 0.916).
Table 1: Quantitative Results
Algorithm R2 No. inputs
P. K. 0.933 7 (c)
PCA 0.916 25 Figure 1: Regression Plots. (a) P.K, (b) PCA, (c) KBest
KBest 0.937 7

5. Conclusions
1. These results show that the concentrations of the main elements for the analized data set can be estimated by using prior knowledge to select
just seven wavelengths.
2. The use of a univariate feature selection algorithm; i.e. Kbest, can even further enhance the performance without increasing the number of inputs
and without prior knowledge of representative wavelengths for each element.

6. References 7. Acknowledgments
This work was supported by Conicyt Project
[1] V. Motto-Ros et al., “Quantitative multi-elemental laser-induced breakdown spectroscopy using
ACM170008. Danny Luarte would also like to
artificial neural networks”, Journal of the European Optical Society, 08011, 2008.
thank the Conicyt Scholarship 2017-21170161.
[2] I.T. Jolliffe , “Principal Component Analysis”, Second Edition, Springer, 2002.
[3] scikit-learn , “Feature Selection: SelectKBest”, [Online]. Available: https://scikit-learn.
org/stable/modules/generated/sklearn.feature_selection.SelectKBest.html