Trends in Analytical Chemistry 100 (2018) 1e6

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Trends in Analytical Chemistry

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Atomic absorption spectrometry e A multi element technique

Sergio L.C. Ferreira a, b, *, Marcos A. Bezerra b, c, Adilson S. Santos a, b,
Walter N.L. dos Santos b, d, Cleber G. Novaes b, c, Olivia M.C. de Oliveira e,
Michael L. Oliveira a, b, Rui L. Garcia e
a
Universidade Federal da Bahia, Grupo de Pesquisa em Química e Quimiometria, 40170-270, Bahia, Brazil
b
Instituto Nacional de Ci^
encia e Tecnologia, INCT, de Energia e Ambiente, UFBA, 40170-290, Bahia, Brazil
c
Universidade Estadual Sudoeste Bahia, 45206-510, Jequi e, Brazil
d
Universidade do Estado da Bahia, 41150-000, Bahia, Brazil
e
Universidade Federal da Bahia, Instituto de Geoci^encias, 40170-290, Bahia, Brazil

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

Article history: In the past, many types of researches have been performed to allow multi-element determinations using
Available online 26 December 2017 atomic absorption spectrometry. The first spectrometers developed for this purpose were proposed in
the 1970s, using flame and furnace atomizers.
Keywords: In the early 2000s, a spectrometer equipped with software that allows a fast selection of the hollow
Atomic absorption spectrometry cathode lamps was introduced commercially. This equipment operates in a sequential mode, and it
Simultaneous determination
enables the determination of up to 16 elements. Many publications have reported its performance.
Sequential determination
Over the years, many spectrometers were built adding new technologies, but they were discontinued
Internal standardization
HR-CS AAS
due to low sensitivity, difficulty for background corrections, etc. However, all the efforts of the past have
contributed to the development and consolidation of the high-resolution continuum source atomic
absorption spectrometry (HR-CS AAS) using flame and furnace atomizers. This technique allows the
establishment of sequential and simultaneous methods for determinations of many elements with high
sensitivity and efficient background correction.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction instrumentations, as opposed to liquid samples [1,4]. FAAS is the

Atomic absorption spectrometry (AAS) is one of the most
commonly used techniques for analytical purposes [1]. It has been
widely used in research laboratories and also in the food, envi-
ronmental, pharmaceutical, petroleum and in other sectors [2e6].
It can be employed by three different atomization processes, which
are: flame atomic absorption spectrometry (FAAS), electrothermal
atomization atomic absorption spectrometry (ETAAS) [5], and
chemical vapor generation atomic absorption spectrometry
(CVG-AAS) [7,8]. However, the choice of the ideal technique is
determined by the analyte's chemical nature and its content in the
sample, as well as the sample's chemical composition and its
physical state. Direct determination of analytes in solid samples
using atomic absorption spectrometry requires specific
* Corresponding author. Universidade Federal da Bahia, Instituto de Química, CEP
40170-270, Salvador-Bahia, Brazil. Fax: þ55 71 32836831.
E-mail address: slcf@ufba.br (S.L.C. Ferreira).
simplest and most widely used approach, although the sensitivity is
the smallest among all others. ETAAS also has excellent applica-
bility, as it allows the direct analysis of solid samples, and it has a
higher sensitivity than FAAS. However, it requires an efficient
optimization of the temperature program and choice of the
chemical modifier to obtain valid results [1,9]. CVG-AAS has
excellent sensitivity, and, in the past, it has been restricted to some
elements (arsenic, antimony, selenium, bismuth, cadmium, lead,
etc.). Currently, many researchers have developed works to extend
the applicability of this technique for the determination of other
chemical elements [10]. Cold vapor-AAS has a restricted use for the
determination of mercury and cadmium [11,12]. It has an excellent
sensitivity and it is one of the most recommended methodologies
for the determination of mercury.
Despite all of these advantages and applications, the fact that AAS
was not a multi-element technique was its main limitation in the
past. Simultaneous or sequential methods could not be established.
Also, the internal standardization technique, which is often recom-
mended for corrections of matrix interferences, could not be used.

https://doi.org/10.1016/j.trac.2017.12.012
0165-9936/© 2017 Elsevier B.V. All rights reserved.
2 S.L.C. Ferreira et al. / Trends in Analytical Chemistry 100 (2018) 1e6

The comparison between inductively coupled plasma optical the simultaneous determination of up to 16 elements using flame
emission spectrometry (ICP OES) and FAAS reveals that: (i) the two and electrothermal atomizers [18]. Afterward, this equipment was
techniques have a similar sensitivity; (ii) the FAAS spectrometer is a employed in the simultaneous determination of nine metals in
cheaper equipment than the ICP OE spectrometer; (iii) the costs of manganese nodules using air-acetylene flame. The results showed
gas consumption to employ FAAS are lower than using ICP OES, efficiency in accuracy and precision comparable to other conven-
even when utilizing nitrous oxide, which is more expensive than tional spectrometric methods [19]. Harnly and Kane also optimized
acetylene; and (iv) both methodologies have allowed the coupling the simultaneous determination of nine elements using this same
with flow injection analysis (FIA), sequential injection analysis (SIA) spectrometer with electrothermal atomization. The parameters
and others flow techniques [13,14]. Also, the comparison between studied were: acid matrix (nitric or hydrochloric acid solution),
ETAAS and inductively coupled plasma mass spectrometry measurement mode (peak height or area), atomizer surface
(ICP-MS) shows compatible results. The sensitivities are similar, but (graphite type), atomization mode (tube wall and platform), and
the gases consumption using ETAAS is much lower than ICP-MS, atomization temperature [20]. Many other works were also
and the ETAAS spectrometer and its maintenance are cheaper developed using this equipment; however, several limitations were
than the ICP-MS spectrometer. However, the optimization step of observed, and the authors concluded that the use of high-quality
the experimental conditions for ETAAS, in some cases, can be more gratings and two-dimensional detectors would be required [21].
complicated when the element is volatile and the matrix is com- In the late 1980s, an atomic absorption spectrometer capable of
plex. The multi-element characteristic of the ICP OES and ICP-MS determining four elements simultaneously with furnace or flame as
has always been the principal advantage in relation FAAS and the atomizer using Zeeman for background correction [22] was
ETAAS, respectively. Table 1 presents the limits of detection for developed. Farah and Sneddon optimized an automated flame/
several elements using FAAS, ETAAS, ICP OES and ICP-MS [15]. furnace spectrometer with the capacity of measuring four elements
simultaneously. They observed that the sensitivity of the multi-
element determination is lower than the single-element determi-
2. First studies e atomic absorption spectrometry as multi- nation [23]. Sneddon et al. published a review article in 1993 pre-
element technique [16] senting the several attempts that were developed aiming the use of
AAS as a multi-element technique [21]. In 1996, Harnly, evaluated
One of the first works established using AAS as a multi-element in detail the potential of an ETAAS spectrometer (prototype) using a
technique was proposed by Salin and Ingle [17]. The equipment was continuous source, which was developed with the advances in the
developed using four hollow cathode lamps, combined with beam fields of the spectrometry and detector technology. The results
splitters, a carbon rod atomizer, a special monochromator with obtained demonstrated that the instrument has the followings
separates slits for each element, and a single photomultiplier tube. characteristics: (i) capacity for multi-element determinations from
Then, the lamps of each element are turned “on” and “off” in a 30 to 40 elements; (ii) wavelength and time-integrated absorbance
sequential manner at the same frequency so that only one lamp is measurements which are independent of the source width; (iii)
“on” at a time. The major limitation of this equipment was the detection limits comparable to line source AAS; (iv) extended
impossibility of using the hydrogen lamp for background correction calibration ranges. Figures of merit obtained for some elements are
since its continuum radiation passes through all slits. The absolute comparable with those found using inductively coupled plasma
light levels resultant of this approach was considerably lower than mass spectrometer [24]. An electrothermal atomization atomic
the systems developed using a single lamp. Spectral overlap absorption spectrometer with longitudinal Zeeman-effect back-
problems were also observed. Despite this, these differences did ground correction using electrodeless discharge lamps (EDL) and
not significantly affect the limits of detection, sensitivity, precision transversely-heated graphite tube atomizer (THGA), allowed the
and calibration curves in most cases. The authors concluded that, development of multi-element determinations. This instrument
after an instrumental improvement, this system could allow the was made commercially available but was later discontinued [25].
determination of six to eight elements routinely [17]. Harnly et al. In the early 2000s, a company introduced a flame atomic ab-
developed the first atomic absorption spectrometer using xenon sorption spectrometer, which works in fast sequential mode, fitted
arc lamp (300 W) as a continuum source. This instrument allowed with a deuterium background corrector, automatic switching of
hollow-cathode lamps, and programmable gas control that enables
automatic set-up and change-over of gas flow. The use of 4 multi-
Table 1
Limits of detection (mg L1) from spectrometric techniques for some elements [15]. element lamps allows the determination of up to 16 elements.
However, during the analytical measurements, the burner height is
Element FAAS ETAAS* ICP OES ICP-MS
fixed. Thus, the optimization of this parameter has been made
Ag 3 0.02 0.2 0.003 considering either the analyte of lower sensitivity in AAS, or the one
Al 30 0.2 0.2 0.06
with the lowest concentration in the analyzed matrix. This equip-
Ba 20 0.5 0.01 0.002
Ca 1 0.5 0.0001 2 ment has had an excellent commercial acceptance, and several
Cd 1 0.02 0.07 0.003 works have been developed using this instrument [26e33]. Projahn
Cr 4 0.06 0.08 0.02 et al. proposed the use of the internal standardization technique in
Cu 2 0.1 0.04 0.003 flame atomic absorption spectrometry using this spectrometer
Fe 6 0.5 0.09 0.45
K 2 0.1 75 1
[26]. Cassella et al. determined sequentially calcium and magne-
Mg 0.2 0.004 0.003 0.15 sium in biodiesel using a single solution of the sample [27]. Pereira
Mn 2 0.02 0.01 0.6 determined sequentially cadmium, copper, and lead in tea leaves
Mo 5 1 0.2 0.003 employing thermospray-FAAS [28]. Another method was proposed
Na 0.2 0.04 0.1 0.05
for sequential determination of arsenic and antimony, bismuth, and
Ni 3 1 0.2 0.005
Pb 5 0.2 1 0.007 lead by HG AAS [29]. Ferreira et al. developed an analytical strategy
Sn 15 10 1 0.02 using slurry sampling for the determination of copper, manganese
V 25 2 8 0.005 and iron in seafood [30]. Some methods have also been established
Zn 1 0.01 0.1 0.008 using the internal standardization [27,31e33]. Table 2 reports some
Obs: *Values based on a 10 mL sample volume. analytical methods developed using this spectrometer.
 S.L.C. Ferreira et al. / Trends in Analytical Chemistry 100 (2018) 1e6 3

Table 2 determined in the primary absorption line (228.802 nm), and iron
Analytical methods developed using FS-FAAS with line source. with content in the (mg Kg1) range was quantified in the adjacent
Analytes Sample Use of the technique References secondary line (228.726 nm). The sensitivity ratio between these
Au, Cu, Mn, Fe, Scrap wood digested Tl and Bi evaluated as [26]
two lines is 110 [1]. The tungsten-iridium permanent modifier and
Zn and Mg and copper rich reference elements the difference in volatility of the two analytes allowed a tempera-
matrix ture program of 700 C for pyrolysis temperature and 1700 C and
Ca and Mg Biodiesel Co as internal standard [27] 2600 C for cadmium and iron atomization temperatures, respec-
Cd, Cu and Pb Tea Leaves Sample introduced as a [28]
tively [38]. Ferreira et al. optimized a method for the simultaneous
slurry
As and Sb, Bi Several samples Hydride generation as [29] determination of cadmium, iron, and tin in canned food. The ab-
and Pb way to introduce the sorption lines established were 228.802 nm (primary line for cad-
sample mium), and the adjacent secondary lines (228.725 nm) and
Cu, Mn and Fe Seafood samples Sample introduced as a [30]
(228.668 nm) for iron and tin, respectively. The relative sensitivities
slurry
Fe and Mn Wine Cobalt, silver, nickel [31]
are 35 for tin and 110 for iron [1], which were compatible with the
and indium tested as contents of the three elements in the analyzed matrices [39].
reference elements Resano et al. developed an analytical strategy for the simultaneous
Cu Sugar cane spirits Ag, Bi, Co and Ni were [32] determination of cobalt, iron, lead and nickel in solid samples of
evaluated as internal
carbon nanotubes. The atomic lines chosen were 283.245 nm for
standards
Cd, Co, Cr, Cu, Organic fertilizers Ultrasound-assisted [34] iron, 283.306 nm for lead, 283.393 and 283.443 nm for cobalt and
Mn, Ni, Pb extraction in a cup-horn 283.455 nm for nickel. The amount of chemical modifier required
and Zn sonoreactor for the procedure was optimized for lead due to the high volatility
of this element. The atomization temperature in 2500 C allowed
the determination of the four elements, generating well-defined
unimodal peaks for all the analytes. However, this atomization
3. High-resolution continuum source AAS as multi-element
temperature caused a loss of sensitivity of approximately 30% for
technique
lead [40]. Simultaneous determination using HR-CS GFAAS has the
following advantages: an increase in the analytical frequency of the
High-resolution continuum source atomic absorption spec-
method and a lower consumption of graphite tube because a single
trometry (HR-CS AAS) has often been employed as a multi-element
temperature program can enable the determination of two or more
technique [1,35,36], allowing sequential and simultaneous deter-
elements. In view of these advantages, many methods have been
mination of chemical elements from the same sample aliquot [9,37].
proposed involving simultaneous determinations of metals using
The first works published were developed using prototypes by the
HR-CS GFAAS, which includes cadmium and iron in sewage sludge
research groups of Becker-Ross and Welz [37]. In 2003, a spec-
[41], molybdenum and titanium in biological fluids [42], nickel and
trometer equipped with a flame atomizer was commercially intro-
vanadium in crude oil [43], molybdenum and nickel in wine and
duced. Another equipment was available by the same company in
soil amendments [44], cobalt and nickel in vitamin B12 [45], cobalt,
2007, which has presented graphite furnace and flame atomizers in
aluminum and iron in waste water [16], iron and nickel in fluo-
two separate sampling compartments. These instruments were
ropolymers [46], nickel and iron in vegetables [47], rhodium and
built using a high-intensity xenon short-arc lamp as continuum
ruthenium in spiked river water, road runoff, and municipal sewage
radiation source, a high-resolution double-echelle monochromator,
[48], copper and iron in flours [49], and vanadium, nickel and iron
and a CCD array detector. Several authors have reported details of
in fuel fly ash [50]. Table 3 shows analytical characteristics of
the manufacturing of these spectrometers [1,9,36].
simultaneous methods using HR-CS GFAAS for the determination of
metals in several matrices.
3.1. Simultaneous determination employing HR-CS GFAAS
3.2. Sequential determination using HR-CS AAS
The simultaneous determination using HR-CS AAS requires the
use of graphite furnace as an atomizer, where two or more chemical Sequential determinations employing HR-CS AAS can be
elements are determined in the same aliquot of a solution or the developed using flame or graphite furnace as atomizer. For this, a
same mass. The quantification for two elements is possible when fast change of the wavelengths enables the quantification of more
the absorption line of the second appears within the spectral range than one element in a single portion of the sample [9,36].
that reaches the CCD array detector, which is in between about 0.2 The optimization of the instrumental conditions in the methods
and 1 nm, depending on the wavelength range [36]. Also, the two established using flame is quite simple, and the operator must
absorption lines established for the simultaneous determination choose the lines according to the contents of the elements in the
must be compatible with the concentrations of the two elements in studied matrix. Ferreira et al. determined calcium and magnesium in
the samples which will be analyzed. Additionally, the thermo- dairy products using the secondary lines 239.856 nm (relative
chemical behaviors of the target elements should be evaluated. So, sensitivity 140) and 202.852 nm (relative sensitivity 23), respec-
elements with similar thermochemical properties require a tively. These lines were selected because the contents of these ele-
chemical modifier that is adequate for all of them, and the estab- ments in the samples are at the level of mg analyte per gram of
lishment of a temperature program could be a simple task. How- sample. In this method, the sample has been aspirated as a slurry,
ever, for target elements with different thermochemical behaviors and the quantification of the elements has been performed using the
(e.g., one volatile and the other refractory), the development of the external calibration technique [51]. Other methods have also been
temperature program could be more difficult. In this case, the proposed using HR-CS FAAS, such as antimony and lead in pewter
amount of the chemical modifier should be sufficient to stabilize alloys [52]; copper, iron, nickel and zinc in vegetable oils [53]; cad-
the most volatile element and avoid the over stabilization of the mium and lead in water [54]; copper, zinc, manganese and magne-
most refractory [36]. Welz et al. developed the first method using sium in beverages, herbal infusions and dietary supplements [55].
HR-CS ETAAS for simultaneous determination of two metals [38]. In Sequential determination of chemical elements using HR-CS
this, cadmium in the (mg Kg1) concentration range was GFAAS requires care during the optimization of experimental
4 S.L.C. Ferreira et al. / Trends in Analytical Chemistry 100 (2018) 1e6

Table 3
Simultaneous determination of metals in several samples using HR-CS GFAAS.

Analytes Sample Wavelength's Pyrolysis Atomization References

temperature ( C) temperature ( C)

Cd, Fe, Sn Canned food. 228.802 nm (Cd), 228.725 nm (Fe) 228.668 nm (Sn) 700 2550 [39]
Co, Fe, Ni, Pb Carbon nanotubes 283.245 nm (Fe), 283.306 nm (Pb), 800 2500 [40]
283.393 nm (Co), 283.455 nm (Ni)
Mo, Ti Biological fluids 319.200 nm (Ti) and 319.397 nm (Mo) 1400 2650 [42]
Ni, V Crude oil 305.432 nm (V) and 305.633 nm (V) 1000 2650 [43]
Mo, Ni Wine/soil 313.259 nm (Mo), 313.410 nm (Ni) 1200 2650 [44]
Al, Co, Fe Water 237.312 nm (Al), 237.386 nm (Co), 237.362 nm (Fe) 800 2100 [16]
Ni, Fe Polymers 232.003 nm (Ni), 232.036 nm (Fe) 800 2300 [46]
Rh, Ru Several samples 343.489 nm (Rh), 343.674 nm (Ru) 1400 2400 [48]
Ni, Fe Vegetables 232.003 nm (Ni), 232.036 nm (Fe) 1400 2500 [47]
Cu, Fe Flours 217.894 nm (Cu), 217.812 nm (Fe) 1400 2400 [49]
V, Ni, Fe Fuel fly ash 294.236 nm (V), 294.391 nm (Ni), 294.235 nm (Fe) 1350 2650 [50]

conditions. In this case, the target elements may have atomic lines
of different wavelengths, and the temperature program can have
more than one atomization temperature. Therefore, the choice of
the chemical modifier is critical for the efficiency of the method
developed. Generally, the atomization temperature of the most
volatile element is the same as the pyrolysis temperature of the
least volatile one. Ferreira et al. quantified cadmium and lead in
organic pharmaceutical formulations. In this, the element contents
in the matrices are very low, requiring high sensitivity. Both
elements are volatile but are efficiently stabilized using an acid
mixture palladiumemagnesium as a chemical modifier. The tem-
perature program for cadmium was established using the pyrolysis
and atomization temperatures of 800 C and 1400 C, respectively,
and an atomization temperature of 2000 C for lead [56]. Other
analytical strategies employing sequential determination by HR-CS
GFAAS include manganese and chromium in vegetable oil, and
biodiesel [57], cadmium and chromium in yerba mate [58] and in
tannin samples [59].
Methods concomitantly employing sequential and simulta-
neous determination have also been proposed. Welz et al. devel-
oped an analytical strategy for quantification of cadmium,
chromium, iron, and aluminum. Firstly, cadmium was determined
in the atomic line 228.802 nm using pyrolysis and atomization
temperatures of 800 C and 1700 C, respectively. Afterwards,
chromium, iron, and aluminum were determined in the lines
425.433 nm, 425.076 nm, and 425.315 nm, respectively, utilizing
2600 C as the atomization (Cr and Fe) or vaporization (AlH)
temperature. A single sample aliquot allows the determination of
the four metals [60]. Teixeira et al. developed a method using
sequential and simultaneous strategies for the determination of
lead, copper, and iron in ethanol fuel. Firstly, the lead was deter-
mined at 217.000 nm, using pyrolysis and atomization tempera-
tures of 850 C and 1400 C, respectively. Then, the others metals
were simultaneously determined in a single sample aliquot using
the wavelengths of 216.509 nm for copper and 216.455 nm for iron,
utilizing an atomization of 2400 C for both elements [61]. Table 4
shows instrumental conditions of some methods proposed for
sequential determinations by HR-CS GFAAS.
4. Internal standardization technique using atomic
absorption spectrometry
Internal standardization is the most promising approach to
correct matrix effects during the development of analytical
methods. It is a technique widely used in ICP's and chromato-
graphic methods due to the multi-element characteristic of these
methodologies. In the past, the inability of the AAS to measure
simultaneously or sequentially more than one element prevented
the use of internal standardization. However, the development of
multi-element spectrometers enabled the use of internal
standardization in AAS, allowing the corrections of errors from
matrix effects and improving precision and accuracy of methods
arising from:
(i) Variations in the aspiration rates of the samples and cali-
bration standards, due to differences in the viscosity and
surface tension of the solutions involved in the experiments,
which affects the transport efficiency during the analytical
measurements.
Pereira et al. evaluated the employment of silver, nickel, cobalt,
and bismuth as an internal standard for the determination of
copper in sugar cane spirits employing FS-FAAS. This matrix has an
alcohol content in the range from 30 to 60% (v/v), and silver is
efficient to eliminate the transport interference, enabling precise
and exact results [32].
(ii) Changes in the analytical signals obtained during the atom-
ization process due to great differences in the chemical
composition of the samples and the calibration standards,
thus making it difficult to use the external calibration
technique.
Ferreira et al. proposed a method for the direct determination of
iron and manganese in wine using FS-FAAS. The elements cobalt
and indium as internal standards have been efficient to correct the
interference due to the high content of organic compounds in the

Table 4
Sequential determination of metals in several samples using HR-CS GFAAS.

Analytes Sample Wavelength's Temperature program ( C) References

Cd, Pb Organic drugs 228.802 nm (Cd), 217.001 nm (Pb) 800 py-t for Cd, 1400 at-t for Cd, 2000 at-t for Pb [56]
Mn, Cr Vegetable oil and biodiesel 279.482 nm (Mn), 357.868 nm (Cr) 800 py-t for Mn, 1500 at-t for Mn, 2500 at- for Cr [57]
Cd, Cr Yerba mate 228.802 nm (Cd); 357.869 nm (Cr) 450 py-t for Cd, 1500 at-t for Cd, 2500 at-t for Pb [58]
Cd, Cr Tannin 228.802 nm (Cd); 357.869 nm (Cr) 400 py-t for Cd, 1500 at-t for Cd, 2500 at-t for Pb [59]

(py-t) e Pyrolysis temperature, (at-t) e atomization temperature.

 S.L.C. Ferreira et al. / Trends in Analytical Chemistry 100 (2018) 1e6
wine matrix; it improves the accuracy and precision method,
allowing the use of the external calibration technique [31]. Neto
et al. determined lead in 22 different matrices employing LS GFAAS,
LS FAAS and HR-CS FAAS using bismuth as internal standard. The
results showed that bismuth corrected interference from the
matrices, improving precision and, in some cases, allowing
accuracy. This efficiency can be explained by similarities between
the stabilization and atomization mechanisms of lead and bismuth
[62].
5. Conclusions
For a long time, many works were developed aiming to provide
the atomic absorption spectrometry (AAS) as multi-element tech-
nique. Advanced searches involving new optical systems, contin-
uum emission sources, correction of background, atomizer and
detector technology, as well as the constant improvement of the
informatics, enabled the manufacture of several spectrometers by
several companies. These spectrometers were introduced in labo-
ratories, but due to some limitations, many of them were dis-
continued. However, much of these searches developed in the past
were of great relevance for the development of the high-resolution
continuum source atomic absorption spectrometry (HR-CS AAS).
Thus, it appears that HR-CS AAS as a multi-element analytical
technique presents the following advantages: (i) use of a single
source for all elements; (ii) complete visualization of the environ-
ment of the analytical line, enabling superior background correc-
tion by simultaneous measurement of atomic and background
absorption; (iii) fast-system for multi-element determination using
atomic lines, allowing the development of sequential and simul-
taneous strategies and also use of internal standardization tech-
nique; (iv) improvement in the correction of the fine-structured
background using a reference spectrum.
All these advantages led to the consolidation of HR-CS AAS,
which can be seen and concluded from the many articles that have
been published over the recent years.
Acknowledgments
Authors are grateful to the Conselho Nacional de Desenvolvi-
mento Científico e Tecnolo gico, to the Fundaça
~o de Amparo a 
Pesquisa do Estado da Bahia and to the Coordenaç~ ao de Aperfei-
çoamento de Pessoal de Nível Superior for providing grants and
fellowships and for financial support.
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