Electron Probe X-Ray Microanalysis

EPXMA can be performed in (scanning) electron microscopes equipped with a semi-

conductor detector, or in electron microprobe analyzers featuring an ED detector
and one or more WD detection systems.

From: Encyclopedia of Analytical Science (Third Edition), 2019

Related terms:

Chemical Speciation, Sulfate, Oxide, Atomic Number, Chemical Element-

, Bremsstrahlung, Atmospheric Aerosol, Monte Carlo Method

View all Topics

Learn more about Electron Probe X-Ray Micro-

analysis

Microscopy | Biomedical Applications☆

A. Warley, in Encyclopedia of Analytical Science (Third Edition), 2013

Capabilities
EPXMA and EELS are complementary techniques for the study of biological speci-
mens. Of the two EPXMA is much simpler, the focusing of the beam onto the area
of interest producing a spectrum in which the presence, or absence, of an element
of interest is easily determined. All the elements present in the area of analysis
are detected in a single analytical run. This has advantages: it eliminates the need
for sequential screening for different elements and can also reveal the presence of
unsuspected elements. However, it must be realized that the technique can be used
to detect nuclides of elements only, and no information about the chemical state of
the element can be inferred.

EPXMA is capable of providing information with high spatial resolution. In thin

sections (< 100 nm thick), spatial resolutions of the order of 10–20 nm have been re-
ported. This figure depends on many factors such as the type of instrument used, the
internal microscope geometry, the electron emitter, the accelerating voltage, and the
thickness and composition of the specimen. The spatial resolution decreases as the
specimen thickness and/or the mass under the beam increases; the resolution is also
decreased with lower accelerating voltages. A minimum detectable mass of 10− 18 g
of iron has been obtained in a single analytical run of 100 s. However, for biological
applications the minimum detectable concentration of an element in the specimen
mass is more relevant. In a thin section a minimum detectable concentration in the
region of 1 mmol per kilogram of dry mass of the specimen localized under the
beam should be possible with a practical analysis time of 100 s. This sensitivity is
low compared with other techniques, for example, atomic absorption spectroscopy.
In consequence, EPXMA cannot be used for detecting trace amounts of elements
evenly dispersed throughout a matrix.

Although EELS analysis and the associated techniques of EFTEM and ESI have
been considered more difficult to perform than EPXMA, developments both in
instrumentation and software have made these techniques easier to use resulting in
an increase in publications featuring these methodologies especially EFTEM and ESI.
EELS is generally carried out with a field emission source so that probe diameters
of the order of 1 nm can be achieved, making this a very high-resolution method
of analysis. Due to the higher collection efficiency, EELS is also more sensitive
than EPXMA. Recently it has been shown that it is possible to detect single atoms
of iron and calcium in isolated biological macromolecules. As stated previously, the
two techniques are complementary. The elements Na and K, which are important
in many biological systems, are poorly detected in EELS but easily detected with
EPXMA, whereas the superior sensitivity of EELS makes it ideal for the detection of
calcium, which is poorly detected in EPXMA because of overlap of the Ca K by the
K K peak.

> Read full chapter

Film Characterization and Some Basic

Film Properties
Donald M. Mattox, in Handbook of Physical Vapor Deposition (PVD) Processing
(Second Edition), 2010

Electron Probe X-ray Microanalysis (EPMA) and SEM-EDAX

Electron probe X-ray microanalysis (EPMA) uses electrons to excite characteristic
X-rays, which are analyzed for energy or wavelength.[92] Lateral and depth resolution
is approximately 1 micron. This technique detects elements with atomic numbers
greater than 5 and quantitative analysis may be done on atomic numbers greater
than 11. The best analysis is on flat surfaces. Sensitivity is 100 ppm with wave-
length-dispersive spectrometry and 1000 ppm with energy-dispersive analysis. The
technique has poor sensitivity to light elements in a heavy matrix.

The SEM can be used for elemental analysis by using the EDAX mode. In the
SEM-EDAX analytical technique the characteristic X-rays emitted from an elec-
tron-bombarded surface in the SEM are analyzed for their characteristic wavelengths
using a crystal spectrometer to give qualitative elemental analysis (XRF). This tech-
nique allows both the surface morphology and composition to be determined on
the same area.

> Read full chapter

Monitoring of Air Pollutants

Hong Geng, ... Chul-Un Ro, in Comprehensive Analytical Chemistry, 2015

2.1 Fundamentals
Energy-dispersive electron probe X-ray microanalysis (ED-EPMA) appeared when
the use of a solid-state Si(Li) EDX detector in conjunction with an electron micro-
scope was described for the first time in 1968 by Fitzgerald and co-workers [5].
After a while, ED-EPMA based on SEM/EDX became one of the most common,
non-destructive techniques which could provide information on morphology of
(sub)micron individual particles from their secondary or backscattered electron
images, together with information on their chemical compositions from electron-in-
duced, characteristic X-rays of chemical elements in the particles. When ED-EPMA
measurements are performed in an automated, computer-controlled way, then a
significant number of single aerosol particles can be probed in a reasonable analysis
time [6]. After ultrathin window EDX detectors were commercially available in 1990s,
the detection of low-Z elements such as C, N, O and F together with heavier elements
(Z ≥ 11) became feasible in ED-EPMA. However, accurate quantification of the low-Z
elements had been a problem for a long time as the characteristic X-ray lines of the
low-Z elements undergo extremely strong attenuation while propagating through
the particle volume and the conventional correction procedures such as ZAF (atomic
number (Z), X-ray absorption (A) and secondary fluorescence (F) correction) and ( z)
(the X-ray production and absorption as function of mass depth ( z) in the specimen,
where is the sample density and z is the depth of electron penetration in sample)
methods were not sufficient for the accurate estimation of the matrix effect for
the low-Z elements. In 1999, a quantitative ED-EPMA technique based on a Monte
Carlo simulation coupled with successive approximations, called low-Z particle
EPMA, was developed [7]. In the quantification procedure based on the Monte Carlo
calculation, electron trajectories are simulated, and generated characteristic and
Bremsstrahlung X-rays are calculated for spherical, hemispherical and hexahedral
particles sitting on a flat surface, so that the matrix effect of X-ray lines even from
the low-Z elements can be accurately corrected and the concentrations of chemical
elements of single particles can be determined [7,8]. The quantification procedure
provided results accurate within 12% relative deviations between the calculated and
nominal elemental concentrations when the method was applied to various types
of standard particles such as NaCl, Al2O3, CaSO4·2H2O, Fe2O3, CaCO3 and KNO3
[9]. The low-Z particle EPMA has since played important roles in characterisation
of atmospheric aerosols as many environmentally relevant particles contain low-Z
elements in the form of nitrates, sulphates, oxides or mixtures, including a carbon
matrix, and quantitative information is critical for clear chemical speciation of
individual particles [10–13].

Although the quantification procedure based on the Monte Carlo calculation was
originally developed for SEM/EDX applications with a lower accelerating voltage
(10–30 kV), it could also be an excellent tool for the quantitative single-particle
analysis using TEM/EDX at a higher accelerating voltage (200 kV) [14]. In a Monte
Carlo calculation newly modified for TEM/EDX applications, electron trajectories
for a particle sitting on the thin formvar/carbon film (coated on TEM grids) are
simulated and X-rays generated both from the particle and the film can be calculated.
The accuracy of the quantification procedure, including the correction for C and
O X-ray intensities from the formvar/carbon film, was evaluated by comparing
calculated elemental atomic concentrations with nominal ones for 12 types of
standard particles. The relative differences (denoted as Δ) between the calculated
and nominal elemental atomic concentrations are within 18% with the smallest
4.4% (ΔK in KCl) and the biggest 17.4% (ΔC in CaCO3) for electron beam refractory
particles such as NaCl, KCl, SiO2, Fe2O3, Na2CO3, CaCO3, Na2SO4, K2SO4 and CaSO4,
which is sufficiently accurate for the reliable identification of chemical species in
these particles (Figure 1). Intense and high-energy electron beams can cause oxygen
depletion for nitrates or sulphates through decomposition into (NO2 + O−) and
( + O) or yielding sulphites , respectively [6]. Hence, for electron-beam-sensitive salt
particles, such as NaNO3, Ca(NO3)2·4H2O and (NH4)2SO4, the high electron energy
and current employed in TEM/EDX measurements lead to large deviations (>30%)
in quantification.
Figure 1. Transmission electron microscopy images and X-ray spectra of typical KCl,
Na2CO3, NaNO3 and (NH4)2SO4 standard particles.

Reprinted with permission from Ref. [14], Figure 5, p. 8. Copyright (2010) John Wiley
and Sons.

> Read full chapter

X-Ray Absorption and Diffraction |

Overview
Freddy C Adams, in Encyclopedia of Analytical Science (Third Edition), 2019

Electron- and proton-induced x-ray emission

X-rays can be used to create inner-shell vacancies in sample atoms, but charged
particles (in practice, electrons in the 5–100 keV range and protons in the 2–3 MeV
range) can also be employed. EPXMA can be performed in (scanning) electron
microscopes equipped with a semiconductor detector, or in electron microprobe
analyzers featuring an ED detector and one or more WD detection systems. Because
of the more intense bremsstrahlung, detection limits of EPXMA are in the range
0.1%–1%.
If protons are used instead of electrons, a much higher sensitivity can be achieved (μg
per g level for elements lighter than calcium). The microscopic variant Micro-PIXE
employs a focused proton or other heavy particle beam of (sub)-micrometer dimen-
sions for recording maps of elemental species in materials of different kinds.

> Read full chapter

Substrate (“Real”) Surfaces and Surface

Modification
Donald M. Mattox, in Handbook of Physical Vapor Deposition (PVD) Processing
(Second Edition), 2010

2.4.1 Elemental (Chemical) Compositional Analysis

The chemical composition of the surface is important to the nucleation and interface
formation stages of film growth (Ch. 10). For example, the presence of a hydrocarbon
contaminant on the surface can prevent the chemical interactions desirable for
obtaining a high nucleation density during film deposition. In addition, the chemical
composition can have an effect on the strength of the interface and thus the
adhesion.

The analysis of the chemical composition of a surface is done using surface-sensitive

elemental analysis techniques. There are a number of surface analysis techniques
including those involving probing species of electrons (Auger electron spectroscopy
– AES), ions (ion scattering spectroscopy – ISS, and secondary ion mass spectroscopy
– SIMS) and photons (X-ray photoelectron spectroscopy – XPS). In some cases, the
nature of the chemical bonding of the surface atoms is determined using XPS or
IR spectroscopy (FTIR). Generally only the first few atomic layers on the surface are
important to the nucleation of the depositing film material but the near-surface
region may be important to interface formation. Analytical techniques for analyzing
the composition of the near-surface region include Rutherford backscattering spec-
troscopy (RBS) (Sec. 11.5.10), nuclear reaction analysis (NRA), electron probe X-ray
microanalysis (EPMA) and SEM-EDAX.

The problem with many of these analytical tools is that they can only sample a
small area of the substrate, whereas local problems, such as surface inclusions which
generate pinholes in the deposited films, may be restricted to a small area and easily
missed.

Auger Electron Spectroscopy (AES)

Auger electron spectroscopy is a surface-sensitive analytical technique that utilizes
the Auger electrons that are emitted from a surface when it is bombarded (excited)
by an incident high energy (1–30 keV, 0.05–5 microamps) e-beam. The ejected
Auger electrons have characteristic energies (few tens of eV for light element KLL
electrons to 2000 eV for heavy element MNN electrons) and these energy peaks
are superimposed on a continuum of electron energies in the analyzed electron
energy spectrum. These peaks can be resolved by double differentiation of the
electron energy spectrum. Figure 2.7 shows the “raw” electron energy spectrum and
the Auger spectrum after the background spectra have been eliminated. Energetic
electrons rapidly lose energy when moving through a solid so the characteristic
energy of the Auger electrons is only preserved if the electrons escape from the
first few monolayers (MLs) (< 10 Å) of the surface (“escape depth”), so AES is a very
surface-sensitive analytical tool. In-depth profile analysis can be made by eroding
the surface by sputtering or chemical means and analyzing the new surface.
Figure 2.7. The “Raw” Electron Spectra of a Gas Surface Being Bombarded with
Energetic Electrons (lower) and the Auger Electron Spectra after the Background has
been Eliminated (upper)

Auger electrons are not emitted by helium and hydrogen and the sensitivity increas-
es with atomic number. The detection sensitivity ranges from about 10 at% (atomic
per cent) for lithium to 0.01 at% for uranium. Auger electron spectroscopy can detect
the presence of specific atoms but to quantify the amount requires calibration stan-
dards that are close to the composition of the sample. With calibration, composition
can be established to ±10%. Where there is a mixture of several materials, some of
the Auger peaks can overlap, but by analyzing the whole spectrum the spectrum can
be deconvoluted into individual spectra.

Electron beams can be focused to small diameters so AES can be used to identify
the atomic content of very small (submicron) particles as well as extended surfaces.
The secondary electrons emitted by the probing electron bombardment can be used
to visualize the surface in the same manner as scanning electron microscopy (SEM).
Thus, the probing beam can be scanned over the surface to give an SEM micrograph
of the surface and also an Auger compositional analysis of the surface.

In PVD processing, AES is used to establish the reproducibility of the chemistry of

the surface of the as-received substrate material, the effect of surface preparation on
the substrate surface chemistry, and the composition of the surface of the deposited
film. Profiling techniques can be used to determine the in-depth composition and
some information about the interfacial region.

Ion Scattering Spectroscopy (ISS) and Low Energy ISS (LEISS)

Ion scattering spectroscopy (ISS) and low energy ISS (LEISS) are surface-sensitive
techniques that take advantage of the characteristic energy loss suffered by a low
energy bombarding particle on collision with a surface atom. The low energy of the
impinging and scattered ions differentiates them from high energy ion scattering
used in RBS (Sec. 10.5.10), which penetrates deeply into the solid. The energy loss
of the reflected particle is dependent on the relative masses of the colliding particles
and the angle of impact, as given by Eq. 2.2 and Figure 2.8.
Figure 2.8. Collision of Particles and the Transfer of Momentum

From the Laws of Conservation of Energy and the Conservation of Momentum, the
energy, Et, transferred by the physical collision between hard spheres is given by:

(2.2)

where

i = incident particle
t = target particle
E = energy
M = mass
is the angle of incidence as measured from a line joining their centers of
masses

The maximum energy is transferred when cos = 1 (zero degrees) and when Mi =
Mt.

Most commercial ISS equipment only analyzes for charged particles, and particles
that are neutralized on reflection are lost. The energy of the scattered ion is typically
analyzed by an electrostatic sector analyzer or a cylindrical mirror analyzer. Ions for
bombardment are provided by an ion source. Depth profiling can be done using
sputter profiling techniques.

Ion scattering spectrometry is capable of analyzing surface species with detection

limits of >0.1 at% for heavy elements and >10 at% for light elements. Mass resolu-
tion is poor for mixtures of heavy elements, and surface morphology can distort the
analysis results since the scattering angle can change over the surface.

Secondary Ion Mass Spectroscopy (SIMS)

Secondary ion mass spectroscopy (SIMS) is a surface analytical technique that utilizes
the sputtered positive and negative ions that are ejected from a grounded surface
by ion bombardment. The ejected ions are mass-analyzed in a mass spectrometer.
The ions may be in an atomic or molecular form and may be multiply charged.
For instance, the sputtering of aluminum with argon yields Al+, Al2+, Al3+, Al2+, and
Al3+. When molecules are present, the sputtering produces a complex distribution
of species (cracking pattern). The technique can analyze trace elements in the ppm
(parts per million) and ppb (parts per billion) range.

The degree of ionization of the ejected particles is very sensitive to surrounding

atoms (“matrix effect”) and the presence of more electronegative materials such as
oxygen. For example, the aluminum ion yield per incident ion from an oxide-free
surface of aluminum is 0.007, but if the surface is covered with oxygen the yield is
0.7. To quantify the analysis requires the development of standards. The problem
of low ion yield and matrix effect can be avoided by post-vaporization ionization of
the sputtered species. This technique is called secondary neutral mass spectrometry
(SNMS). Since the detected species are sputtered from the surface, the technique is
very surface-sensitive. The matrix effect and the ability of atoms to move about on the
surface makes sputter profiling through an interface with SIMS very questionable.
Since ion beams cannot be focused as finely as e-beams, the lateral resolution of
SIMS is not as good as that of AES.

> Read full chapter

Atomic Spectrometry | Chemometric

Approaches to Data Evaluation
Jose M. Andrade, ... Rosa M. Soto-Ferreiro, in Encyclopedia of Analytical Science
(Third Edition), 2019

Quantification Approaches
Common strategies to quantify species by atomic spectrometry imply obtaining
optimum atomic peaks and regressing them (either the heights or areas) against
the concentrations of their calibration solutions. However, classical (univariate) least
squares regression requires the analytical signal not to be affected by concomitants
or other interfering effects. In other words, the signal must be as specific as possible,
but for an eventual constant background. Here, traditional calibration (including
calibration with external standards and the internal standard approach) will not be
reviewed, just stress that in order to apply them, the signal must necessarily not be
interferred.

Unfortunately, many complex materials present interferences that cannot be avoided

or corrected for, even after their sample treatment. Hence the method of standard
additions (SAM) arises as an alternative to handle out problems. Dissapointingly,
SAM may not account for all relevant troubles.8 Furthermore, the incorrect extrapo-
lation carried out usually to predict the concentration of the test solutions increases
the associated error of the prediction and, so, the confidence interval associated to
the quantification.9

To circumvent many problems related to traditional calibration, isotope dilution

mass spectrometry (ID-MS) is a good alternative. Remarkably, ID-MS is an absolute
method of analysis whose operation can be completely understood and described
by a measurement equation. Combined with inductively coupled plasma-mass
spectrometry (ID-ICP-MS), it constitutes a powerful, primary methodology based on
the measurement of isotope ratios. It is a time-efficient alternative as it avoids
external calibration (i.e., the preparation of a series of calibration solutions) and
compensates for matrix interferences. In this sense, it can be considered a one-point
internal-calibration method, providing far superior data quality than traditional
procedures that do not use isotopic information.10

The Need for Multivariate Calibration

A huge amount of work, time and resources are spent on laboratories to isolate
the signal caused by the analyte(s) from other signals due to the matrix and/or
the analytical protocol (include here, sample treatment and the like). A key idea we
would stress here is that it is possible to change the paradigm. From the “labo-
ratory-achieved-specificity” (required for a unique atomic signal: integrated signal,
maximum height, etc.) to the “mathematically-extracted-specificity” that advanced
regression methods can deliver using the whole atomic signal.

As an example, it is quite obvious that ETAAS measurements are multivariate in

their very nature. First, the “atomic peak” is composed of a series of values. Second,
the overall atomic signal is—strictly speaking—a sum of the different signals that
may occur due to the atomization of volatile components of the sample, molecular
fragments, scattered radiation, volatile forms of the analyte, the atomization of the
analyte itself, atomization of refractory species, etc. Therefore, the signal cannot be
attributed only to the analyte (not even the integrated area). Traditional univariate
calibrations consider only a minor amount of that signal and discard most of its
information.

In the last years, it became recognized that univariate calibration is often more a con
than a pro and different types of multivariate calibration were considered instead.
This is the case for ICP (optical and mass detection), LIBS and several techniques
for analyzing directly solid samples (X-ray fluorescence, EPXMA—electron-probe
X-ray microanalysis-, and laser ablation-ICP-MS). Three recent general reviews (see
Table 8) collected more than 110 applications dealing with the combination of
several multivariate regression methods and several atomic techniques.

Table 8. Applications of multivariate regression to atomic spectrometry

Partial least squares

FAAS Spectrochim. Acta A (2015) 145,
54–62
ETAAS Anal. Chem. (2003) 75, Anal. Methods (2013) 5(16),
5254–5261 4036–4046
ICP-OES Talanta (2010) 82, 1254–1260 Microchem. J. (2016) 129,
231–235
LIBS Soil Sci. Soc. Am. J. (2009) 73 J. Agric. Food Chem. (2012)
1469–1478Chem. Geol. (2010) 60, 718–724Talanta (2012) 110,
277, 137–148J. Anal. At. Spec- 108–117Food Chem. (2016) 212,
trom. (2010) 25, 1733–1738- 183–188Spectrochim. Acta B
Soil Sci. (2010) 175, 447–452- (2016) 115, 40–45Spectrochim.
Anal. Bioanal. Chem. (2011) Acta B (2016) 122, 9–14App.
400, 3315–3322App. Spectrosc. Spectrosc. (2017) 71, 567–582-
(2011) 65, 1197–1201Icarus Food Res. Int. (2017) 94, 72–78
(2011) 215, 608–627J. Anal. At.
Spectrom. (2011) 26, 536–541
XRF Anal. Chim. Acta (2012) 729, Anal. Chim. Acta (2013) 773,
21–25Adv. Mat. Res. (2013) 705, 37–44Food Chem. (2016) 196,
70–74X-Ray Spectrom. (2013) 1023–1030
42, 183–188
Reviews Anal. Chim. Acta (2013) 780, 13–19J. Anal. At.
Spectrom. (2013) 28, 1814–1869J. Anal. At. Spec-
trom. (2014) 29, 1516–1563J. Anal. At. Spectrom.
(2016) 31, 1706–1755J. Anal. At. Spectrom. (2016)
31, 2114–2164
Artificial neural networks
FAAS Microchim. Acta (2007) 158, Curr. Microwave Chem. (2014)
247–253 1(1), 16–21
ICP-OES/ICP-MS Chin. J. Chem. (2007) 25, J. Appl. Spectrosc. (2013) 80,
1658–1662J. Univ. Sci. Technol. 403–413
Beijing (2008)15, 367–374
LIBS Spectrochim. Acta B (2008) 63, Talanta (2012) 110, 108–117-
1216–1220Spectrochim. Acta Appl. Optics (2012) 51,
B (2009) 64, 565–572.- B108–B114Spectrochim. Acta B
Proceedings of SPIE 7854 (2014) 99, 52–58Spectrochim.
(2010, Infrared, Millimeter Acta B (2015) 112, 1–5Anal.
Wave, and Terahertz Technolo- Methods (2016) 8, 1674–1680-
gies), 78543Q/1-78543Q/8En- Energy and Fuels (2017) 31,
ergy and Fuels (2010) 24, 3849–3855
510–517Icarus (2011) 215,
608–627Proceedings of SPIE
(2011, 21st International Con-
ference on Optical Fiber Sen-
sors), 77,532 K/1-77,532 K/4
Support vectors machines
LIBS IEEE Sensors J. (2012)12, J. Anal. At. Spectrom. (2015) 30,
64–70Acta Phys. Sin., (2013) 1541–1551
62(21), 7
Reviews
PLS Regression (Chapter 5), Multivariate Regression Using Artificial Neural Networks and Support
Vector Machines (Chapter 6), Ordinary Multiple Linear Regression and Principal Components
Regression (Chapter 4), in Basic Chemometric Techniques in atomic Spectroscopy (2nd ed.), RSC,
Cambridge, 2013

An issue that requires further study is the need for simple procedures to calculate
figures of merit (performance characteristics) in multivariate regression. IUPAC
presented an approach based on the so-called net analyte signal.11 When ISO and
European Union set new definitions for the (formerly) limits of detection (they
are called now decision limit and capability of detection)12,13 studies were done to
apply those concepts to multivariate regression as simply as possible, which yielded
a straightforward approach to address this issue in a pragmatic, holistic way.14,15 This
is based on the use of the traditional regression among the reference values of the
calibration solutions and the experimental ones derived from the model and the
consideration of the type I and type II errors.

Changing the Paradigm

We usually look for a perfect atomic signal after every developmental step. Many
times, this increases laboratory workloads and expenses. However, other alternative
exists by which an unperfect signal can lead to a satisfactory calibration. If the
equipment is whithin statistical control and leads to reproducible signals, they do
contain the information we are interested at. This is the point: that a suboptimal
atomic signal may be useful. We “only” need to extract its relevant information.

A question arises: what about the concomitants? The answer needs another para-
digm shift: traditional studies about concomitants rely on a one-at-a-time basis. This
involves studying each potential interferent by means of a series of solutions where
the concentration of the suspicious concomitant varies (the others are kept constant).
Conclusions are derived after their measurement. This approach does not consider
interactions between the concomitants and, so, it seems more reasonable to deploy
a formal experimental design to vary all the concomitants simultaneously. Further, if
the standard solutions employed in the experimental design have different amounts
of analyte, they can also be used as calibrators. As they contain “all” the relevant
concomitants the matrix variability inherent to future samples will be present into
the calibration model.

Partial Least Squares

Partial least squares, PLS, is a standard method that leads to satisfactory multivariate
calibrations in many circumstances and can support nonlinearities. Besides, it was
found to be quite robust to common atomization problems. PLS concentrates on
the variables which are more relevant to predict the concentration, so that noisy or
irrelevant variables are discarded.

The use of PLS is exploiting in atomic spectrometry. Despite a handful of pioneering

applications more reports have been published recently, as well as some reviews (see
Table 8), which highlighted the PLS capability to compensate for matrix effects in
both emission and mass spectra.

Regarding AAS, only two references were found since 2007: a comparison of re-
sults obtained using PLS plus FAAS and those from a new method based on the
zero-crossing point-continuous wavelet transformation (an unusual multivariate
regression method) and the determination of Cu by ETAAS in lubricating oils (see
Table 8). For ICP, both optical and mass detection, some applications were reported.
Most applications of PLS were reported for LIBS quantitations, although XRF and
TOF-SIMS (which yield also very complex spectra) benefited from PLS models as
well (see Table 8).

Artificial Neural Networks and Support Vectors Machines

Artificial neural networks (ANNs) and support vectors machines (SVMs) are intended
to address complex calibration problems. The random initialization of the ANNs
make them not too appealing for routine use because the models cannot be re-
produced easily. SVMs avoid this problem and they are becoming popular. Both
methodologies accept any relation (not only a straight one) between the predictors
(spectra) and the concentration(s) of the analyte(s); that is, they can work with noisy
data and can yield good models even when other methods fail. They are robust in
the sense that they support spectral deviations from the calibration data set (e.g.,
different noise distributions, random fluctuations in the signal, etc.).

ANNs imply a great deal of computer work as many trials are needed (usually) to get
a reliable model. Also, a great deal of laboratory work is required to get spectra from
a reasonable number of standards. Further, a chemical interpretation is not possible
currently. In addition, it has been reported fairly frequently that ANNs do not always
outperform other classical methods, typically PLS. Error back-propagation ANNs
(BP-ANNs)16 are nowadays the common choice. The term means that the ANN
develops the model iteratively by propagating back the error, in a two steps cycle.
First, the atomic spectrum enters the input layer of the ANN and is transmited
forward throughout the neural “connections” (synapses) until an output is obtained.
That is compared to the target concentration and an error is derived for each sample.
Here the second phase starts. The errors are then transmitted back from the output
 to each neuron in the hidden layer(s) of the ANN so that each neuron receives only
a portion of the total error signal (in accordance with the relative contribution the
neuron made to the output).17

Only two applications were found in combination with FAAS. ICP-OES is a potential
interesting field for ANNs and, thus, they were employed recently. As for PLS,
LIBS constitutes an outstanding application field for ANNs. Their corresponding
references are cited in Table 8.

As mentioned above, SVMs do not require a random initialisation and rely on two
main working stages18–20: (i) project the original data (i.e., the spectra) into a space
of higher dimension by calculating additional dimensions; this is termed “nonlinear
mapping” or “feature mapping”; and (ii) construct an optimal separating surface
(separating hyperplane or boundary) which maximizes the margin between the groups
of samples. The mathematical functions by which we project the original spectra into
a higher space (feature space) are termed “kernel functions,” among which the most
common ones are the linear and the radial basis functions (RBF). Good news is that
it is not necessary for the analyst to know in advance the mathematical functions
behind the kernel. Once the type of kernel is selected (e.g., linear, RBF or polynomial)
the nonlinear mapping functions are set automatically.

When SVMs are applied for regression they are frequently termed SVM-R or SVR.
They search for an optimal hyperplane so that all samples become enclosed within
it. This yields a sort of “tube” which encloses the calibration points. This notion
resembles the classical least squares fit in univariate regression, which finds a
regression line equidistant from all the experimental data pairs. A very important
task is to avoid overfitting, which may occur easily. Recent reports on SVM applied
to atomic spectrometry were devoted to LIBS implementations (Table 8).

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