Trends in Analytical Chemistry 88 (2017) 62e76

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Trends in Analytical Chemistry

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Determination of sulfur by high-resolution continuum source atomic

absorption spectrometry: Review of studies over the last 10 years
Nil Ozbek a, Asli Baysal b, *
a
Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry, Maslak, 34469 Istanbul, Turkey
b
T.C. Istanbul Aydin University, Health Services Vocational School of Higher Education, Sefakoy Kucukcekmece, 34295 Istanbul, Turkey

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

Article history: Sulfur is one of the most abundant elements on the crust of Earth, and it is an essential element for
Available online 5 November 2016 animals and plants. In addition to playing a vital role in living organisms, it has a very important use in
industry as an ingredient in some chemicals, fertilizers, fungicides, pesticides, pharmaceuticals, and so
Keywords: on. There are limit values for sulfur content in many matrices, which explains why it is important to
Sulfur determine sulfur contents.
High-resolution continuum source atomic
This review aims to give an overview of historical development and importance of sulfur determi-
absorption spectrometry
nation by high-resolution continuum source atomic absorption spectrometry (HR CS AAS). We primarily
Molecular absorption spectrometry
Line-source atomic absorption spectrometry
focus on recent applications and their optimized parameters for the determination of sulfur in many
Diatomic molecule matrices. The application of sulfur determination by HR CS AAS is evaluated and some scientic prop-
erties of sulfur determination by HR CS AAS are also presented.
2016 Elsevier B.V. All rights reserved.

1. Introduction sulfur contents are limited to 0.01e0.03% (w/w) by the American

Sulfur, the 10th most abundant element in the universe [1], is
essential to all living things. It has biological functions and can be
found in all animal/plant tissues. It is present in two of the essential
amino acids and needed for some coenzymes. Although elemental
sulfur is not toxic, many sulfur substances, mainly sulfur oxides,
have negative health effects including bronchoconstriction and
increase asthma symptoms. When sulfur dioxide combines with
water and air, it forms sulfurous acid, the main component of acid
rain, which causes deforestation, detriment of aquatic life, and
corrosion to building materials.
There are certain limits for sulfur contents in various matrices.
For instance, the Environmental Protection Agency is planning to
lower the legal limit of sulfur in gasoline to 10 ppm by January 1,
2017 [2] because combustion of fossil fuels is the primary source of
anthropogenic sulfur compounds released into the atmosphere. In
addition, the level of sulfur is very important in metallurgy because
small changes in the sulfur content affect the physical and chemical
properties of steels and alloys. In many stainless steel compositions,
* Corresponding author. Fax: 90 2124255759.
E-mail address: aslibaysal@aydin.edu.tr (A. Baysal).
Society for Testing and Materials [3]. In addition, sulfur dioxide and
sultes, which even have code names as E220eE228, are generally
used for their preservative effects in foods. The presence of these
chemicals is permitted in a wide range of foods, but their maximum
levels were set by various regulations (i.e., beer and malt beverages,
maximum level: 20 mg L
1; potato-, cereal-, our-, or starch-based
snacks, maximum level 50 mg kg
1; processed nuts, maximum
level 50 mg kg
1; vinegars, maximum level 170 mg kg
1, etc.
Maximum levels are expressed as SO2 and related to the total
quantity) [4]. Sulfur level in wines is also limited (200 mg L
1) [4];
however, free sulfur dioxide content in wine is important for wine
quality [5]. All these limits challenge the analytical capabilities for
sensitive and accurate sulfur measurements.
This review identies and evaluates information on sulfur
determination by HR CS AAS based on the available literature
sources indexed in Web of Science. This method underscores the
basics and parameters of the sulfur determination using molecular
absorption by line source atomic absorption spectrometry (LS AAS)
and molecular absorption by HR CS AAS techniques and briey
discusses the relevance of this approach with regard to impact and
future aspects.

http://dx.doi.org/10.1016/j.trac.2016.09.014
0165-9936/ 2016 Elsevier B.V. All rights reserved.
 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76
2. Analytical methods for the determination of sulfur
Because sulfur contents in various matrices are limited and
important, different methods for the determination of sulfur and
sulfur components are developed. One of the oldest sulfur deter-
mination methods is to precipitate sulfate as barium sulfate and
determine it gravimetrically [6]. Because gravimetric method for
determining sulfates is time-consuming and requires great care,
turbidimetric methods are also proposed to increase the speed and
accuracy [7]. Ripper and Rankine developed the other oldest
methods available in the literature. The Ripper method, which is a
reference method for determining sulfur dioxide concentration in
wine, depends on titration with iodine using starch indicator [5].
The method itself suffers from serious matrix effects, i.e., even in
some wines that have no sulfur dioxide, sample may consume some
iodine leading to false positives. Especially for red wines, blueeblack
color of end point is difcult to see, which can be adjusted by dilu-
tion of sample. However, in a collaborative study, it was proved that
the Ripper method is severely limited by poor precision and large
systematic error [8]. Another reference method for the determina-
tion of sulfur dioxide is the Rankine method that relies on sulfur
dioxide owed to a ask containing hydrogen peroxide where it
reacts immediately to form sulfuric acid, which is titrated with so-
dium hydroxide [9]. This method is laborious and time-consuming
and requires pure chemicals and special glass equipment.
Instrumentally, sulfur can also detected in many matrices by
high-temperature combustion with infrared absorption detection
[10], in which sulfur in sample is completely oxidized to sulfur di-
oxide gas in a tube furnace at 1350 C. Then, this gas stream is
passed through a cell in which sulfur dioxide concentration is
measured by an infrared absorption detector. Ultraviolet visible
(UVevis) spectrometry is also used for sulfur determination [11]
but requires laborious sample preparation step and is affected by
various interferences from other ions [12]. In addition, inductively
coupled plasma mass spectrometry (ICP MS) suffers from the in-
terferences caused by oxygen dimer ions. Because its ionization
efciency is approximately 14% in the plasma, sulfur is one of the
several elements that are particularly prone to isobaric in-
terferences and therefore difcult to measure [13]. Inductively
coupled plasma optical emission spectrometry (ICP OES) is also
challenging because O2 absorbs radiation in the low UV; therefore,
all modern ICP OES instruments present a spectrometer evacuated
or purged with an inert gas (Ar or N2) [14,15]. X-ray uorescence
spectrometry (XRF), which is mostly used for standard methods,
requires matrix matching of samples and standards for accurate
measurement [16]. In addition, the ratio of C, H, and O to sulfur in
sample may affect the accuracy [17]. Ion chromatography (IC) for
sulfur determination [18] is highly sensitive, but sample prepara-
tion step is critical, which requires complete combustion of the
sample that may lead to loss of sulfur in sample [17]. Moreover, the
IC often needs an additional column to be installed. Neutron acti-
vation analysis (INAA) is another method [19], but it also suffers
from poor sensitivity because of short life time and the poor acti-
vation of the radionuclide 37S [20]. Finally, some tandem techniques
such as laser ablation inductively coupled plasma mass spectrom-
etry (LA ICP MS) and liquid chromatography inductively coupled
plasma mass spectrometry (LC ICP MS) were used in recent years.
Comparison of available methods for the determination of sulfur is
given in Table 1.
Various analytical techniques have been applied for the deter-
mination of sulfur in different matrices during the last few decades.
Most of these need laborious sample preparation steps. In addition,
because many methods require samples to be aqueous, sulfur in
solid samples requires to be extracted [28] or digested [29]. Alter-
natively, sample preparation procedures such as solid phase
63
microextraction [30], single-step microwave-assisted acid extrac-
tion [31], and pyrohydrolysis [15] can be applied. Nevertheless,
there are some recent methods that can analyze solid samples
directly including hydrothermal carbonization, wavelength
dispersive X-ray uorescence, and ICP MS with laser ablation [21].
3. Analytical method for sulfur determination by molecular
absorption
Sulfur determination by AAS was not possible because its main
atomic lines are 180.671, 181.974, and 182.565 nm in far ultraviolet
region, out of reach for commercially available instruments. To
reach vacuum-UV region, L'vov used a special apparatus with an
inert purging gas, a vacuum grating monochromator, and a graphite
cuvette [32]. Sulfur determination by conventional AAS was very
complicated to be used in routine analysis. Alternatively, because
the effect of sulfur forms on atomic absorption is well known
[33,34], indirect determination methods, i.e., precipitating barium
sulfate [35] or lead sulfate [36], and determination of barium or
lead in supernatant were used. However, these strategies are highly
laborious and require high selectivity in all reactions [37].
As an alternative, molecular absorption spectrum of sulfur-
containing species were used. The method is based on the forma-
tion of diatomic molecules containing sulfur in atomizer and then
measurement of the molecular absorption at one of its nely
structured rotational lines. In atomic absorption spectrometric
studies, gas-phase combination reactions may cause nonspectral
interferences and every effort is made to prevent them, whereas for
the determination of halogens and sulfur by molecular absorption
spectrometry (MAS), the analyte that is a diatomic molecule needs
to be kept in the gas phase. The most important parameters for
MAS are as follows:
(i) Choice of molecule-forming element to generate a stable
diatomic molecule with the analyte in the gas phase of a ame
or graphite furnace: when selecting the diatomic molecule,
the bond dissociation energy should be high enough
(>500 kJ mol
1) to provide stable molecules in the gas phase
[38].
(ii) Choice of the working wavelength for diatomic molecule: this
should be sensitive enough to detect the analyte in the
sample and far from absorption lines of sample contami-
nants to avoid any spectral interference.
(iii) Optimization of atomizer conditions: ame conditions (ame
type, fuel ow rate, oxidant ow rate, and height of obser-
vation) or graphite furnace program (pyrolysis and molecule
formation temperature, modier presence, deposition of
refractive elements on tube/platform) should be appropri-
ately optimized.
(iv) Amount of molecule-forming element: this should provide
high and stable sensitivity for the maximum expected con-
centration of sulfur. Moreover, the upper limit of the linear
range should be far above the maximum expected analyte
concentration so that all analyte concentrations determined
in the sample fall in the linear range. Otherwise, errors can
occur.
After the above-mentioned parameters are optimized or chosen,
sulfur can be determined appropriately using molecular absorption
by LS AAS or HR CS AAS.
3.1. Sulfur determination by LS AAS
Absorption spectroscopy, which detects small emission signals
in a dark and nonluminous environment, has its own challenges
 64
Table 1
Comparison of some sulfur determination techniques by different methods.

Technique Matrix Determined sulfur form Analysis LOD or Cost Other Ref
time Working range
Advantage Disadvantage

Gravimetric Water Sulfate (SO4 2
) NG $ Easily accessible laboratory - Time-consuming [6]

equipment - Large Errors
Titration Wine Sulfur dioxide (SO2) NG $ Easily accessible laboratory - Matrix effects [9,8]
(Ripper and equipment - Poor precision
Rankine) - Large systematic errors
Turbidimetry Water Sulfate (SO4 2
) NG $$ Small aliquot is used Error magnied when total [7]
amount of sulfate present is
small
Ion Biological samples, Sulfur-containing inorganic NG $$ Highly sensitive - Interferences are affected [18]
chromatography environmental samples, food anions: Sulde (S2
) Sulte - Requires complete
samples (SO3 2
) Sulfate (SO4 2
) combustion of the sample

N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76

Polysulde (Sn 2
) - Additional column needed
Thiosulfate (S2 O3 2
)
Thiocyanate (SCN
)
Dithionate (S2 O6 2
),
Polythionate (Sx O6 2
)
Inductively ICP MS Biological samples, Sulfur-containing anions: S2
, 0.1e100 mg L
1 $$$ - Different ICP-MS instruments - Very expensive instrument [21]
coupled plasma environmental samples, food SO3 2
, SO4 2
and S2 O3 2 were used - Multicollector devices show
samples - High sensitivity get obtained low sensitivity
quadrupole collision cell to - Extra gas adaptation is
ICP-QQQ needed for quadrupole
reaction cell, quadrupole
collision cell or ICP-QQQ
applications
- Interferences are affected
ICP OES Environmental samples, SO4 2
0.5 mg L
1 $$$ - It is available for high content - Matrix effect can be seen [22]
geological samples, of sulfur
food samples
LA ICP MS Geological samples, food Total sulfur, sulfur isotopes 0.001e0.5 mg kg
1 $$$$ - A sensitive and rapid - Methods need homogenous [23e25]
samples analytical method samples
- Direct sampling of solid
materials
- Appropriate standard
reference material is needed,
especially for biological
samples
LC ICP MS Biological samples Sulfur-containing molecules 4
20 mg kg
1 $$$$ - Detection of sulfur isotope in - Difculties of calculation [26]
different biological matrix methodology
- Avoids the use of any - Organic solvents are used
collision gas
- High sensitivity
- Baselines are not affected by
interferences from different
solvents
UVeVIS Air - H2S 1.6e8 g m
3 for SO2 $$ - Semiautomatic method - Laborious sample preparation [11]
- SO2 5-15 g m
3 for H2S - Small amount of reagent and step
sample is used - Various interferences from
other ions
 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76 65

compared to emission spectroscopy. Detecting small reduction of

the radiation over a narrow spectral range in a bright, luminous
[19]

[27] environment is challenging. To eliminate the reduction of radiation

caused by matrix elements and only detect target analyte, line
Suffers poor sensitivity because

- Requires matrix matching of

- C, H, and O to sulfur in sample

source lamps, which emit light of a specic wavelength, are used.
samples and standards for

The advantage of this technique is that only a medium-resolution

of short life time the poor

may affect the accuracy

accurate measurement

monochromator is necessary for measuring AAS; however, usu-

ally a separate lamp is required for each element that has to be
determined, which is a disadvantage.
activation of the
radionuclide37S

LS AAS is generally called as conventional AAS. It has ve main

elements including light source, sample cell, and light measure-
ment components, i.e., monochromator, detector, electronics, and
readout. The two most common line sources used in atomic ab-
sorption are the hollow cathode lamp (HCL) and the electrodeless
- No chemicalephysical pre-

contamination

discharge lamp. It provides high sensitivity and makes atomic ab-

sorption a very specic analytical technique with small spectral
problems and positive/

interference (Fig. 1).

- Direct determination

With conventional AAS instruments, because vacuum-UV re-

negative artifacts

gion is unreachable, molecular absorption spectrum of sulfur-

containing species were used as an alternative. The method is
treatment
- Avoiding

based on the formation of diatomic molecules containing sulfur in

atomizer and then measurement of the molecular absorption at one
of its nely structured rotational lines using deuterium (D2) lamp or
an appropriate HCL (having an appropriate emission line.
$$$

$$$

There are limited number of studies for this method because

there are many drawbacks, as listed below.

(i) Limited number of HCLs and their limited number of atomic

Up to 1 ppm

lines generally prevent to target the most sensitive line for

20 mg g
1

the diatomic molecule.

(ii) Lines isolated from D2 source or secondary lines of HCL
selected for measurement have low emission intensities,
which would cause noise and high limit of detection (LOD).
(iii) Lines isolated from D2 source or secondary lines of HCL may

be in very narrow range of rotational absorption prole for

the analyte-containing diatomic molecule, which would
cause low sensitivity and/or spectral interference.
(iv) The bandwidth of the emission line isolated from D2 lamp is
broader than rotational absorption peak of the analyte-
containing diatomic molecule, which would cause low
sensitivity and/or spectral interference [39].
- Total sulfur

(v) Deuterium background correction cannot deal with any

structured background signal, which is typical for the ab-
sorption spectra of diatomic molecules [40].
- S

Nevertheless, there are some preliminary studies for sulfur

determination by its diatomic molecule's nely structured rota-
tional lines, i.e., germanium monosulde (GeS) [41], tin sulde
(SnS), aluminum sulde (AlS), indium monosulde (InS) [42], and
Petroleum products

carbon monosulde (CS) [43]. The appropriate lines for GeS, AlS,
: Long Analysis Time, : Short Analysis Time.

InS, and SnS were obtained from H2 (285 and 215.2 nm), D2
Hair samples

(257.6 nm), Fe (219.18 nm), Pt (243.7 and 241.8 nm), and W

(273.6 nm) HCLs, respectively, whereas 257.6 nm was isolated from
D2 lamp for CS (Table 2).

Table 2
Summary of literature data on sulfur determination by LS AAS.
$$$: High Cost, $: Low Cost.

Lamp Wavelength (nm) Atomizer Ref

GeS H2 285.0 Graphite furnace [41]

215.2
NG: Not Given.

AlS Fe HCL 219.18 Graphite furnace [42]

InS Pt HCL 243.7 Graphite furnace [42]
241.8
INAA

SnS W HCL 273.6 Graphite furnace [42]

XRF

CS D2 257.6 Graphite furnace [43]

66 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76

Fig. 1. LS AAS setup.

Fig. 2. HR CS AAS setup.

3.2. Sulfur determination by HR CS AAS Table 3

Bond dissociation energies for different sulfur diatomic molecules.

Scientists have always thought the use of continuum sources for Bond dissociation energies (kJ mol
1)
AAS. First trials were conducted in the 1960s, but the instruments SeC 713.4 [5]
were not adequate both optically and electronically to detect and SeH 344 [55]
separate target analytes' absorption from continuum source emis- SeSn 464 [55]
sion [44,45]. In the late 1990s, Becker-Ross group designed and SeGe 551 [55]
SeAl 374 [55]
optimized a HR CS AAS [46,47]. The rst commercial instrument
SeIn 289 [55]
was developed by Analytik-Jena AG in Jena, Germany. A schematic
view of this instrument is shown in Fig. 2. In these instruments, a
special high-pressure xenon short arc lamp operating in a hot-spot
which results in volatile carbon disulde (CS2). Consequently, the
mode has been developed [48]. These lamps emit radiation of in-
analyte, which requires the deposition of refractive carbide ele-
tensity at least in an order of magnitude above that of a typical HCL
ments, is reduced. The importance of this process will be further
over the entire wavelength range from 190 to 900 nm. It also in-
discussed in this review.
cludes a high-resolution double monochromator with a prism
SnS was another diatomic molecule that was found to be useful.
premonochromator, a high-resolution echelle grating mono-
SnS has dissociation energy higher than 464 kJ mol
1 and is mainly
chromator, and a charge coupled device array detector. The atom-
not suitable for this kind of analysis as only diatomic species with
ization systems are the same as that used in classical LS AAS, i.e.,
bond dissociation energies higher than 500 kJ mol
1 are considered
mostly ames and graphite furnaces. As the spectral environment
to be suitable for determination. However, in various studies, SnS
of the analytical line is visible in these instruments and the
has shown better sensitivity results than CS diatomic molecule. It
absorbance spectrum over time is displayed at high resolution, the
has many advantages such as isolated absorption range, which
method development and diagnosis and prevention of in-
prevents spectral interferences. In addition, it has high absorption
terferences become much easier.
coefcient when evaporated/generated in gas phase [53]. However,
The development of high-resolution continuum source atomic
for the evaluation of SnS, addition of Sn to samples was required,
absorption spectrometers, with a resolution (l/Dl) of 175,000 in a
and the amount of Sn becomes an important parameter.
0.3e1.0 nm range, corresponding to a bandwidth below 1.6 p.m. per
Virgilio and Rapaso have investigated the possibility of using SH
pixel, makes it possible to select a very narrow wavelength over-
(hydrogen monosulde) lines [54] and found out that CS lines have
lapping the exact molecular absorption of diatomic molecule
better sensitivity and higher signal/noise ratio. Therefore, uncer-
without any restriction. In addition, it is possible to detect spectral
tainty of measuring SH species is higher than that of CS, so usage of
neighboring environment and measure spectral interferences [48].
SH lines was not recommended. The bond dissociation energies for
With the capabilities of these instruments, for elements that are
possible sulfur diatomic molecules are given in Table 3.
nondetectable by conventional AAS, such as S [49], F [50], Cl [51],
and Br [52], due to their absorption lines' location (vacuum-UV
section), determinations become possible by their diatomic lines 4. Optimization parameters of sulfur determination by HR CS
molecular absorptions. In various studies, mainly CS is used for AAS
sulfur determination as a diatomic molecule. Diatomic species with
bond dissociation energies higher than 500 kJ mol
1 are considered 4.1. Selection of wavelength
to be suitable for the determination of nonmetals by their molec-
ular absorption. Because CS has a relatively high bond strength of The most important parameter for sulfur determination by
713.4 kJ mol
1, it is an excellent diatomic molecule for S de- molecular absorption is selecting the appropriate wavelength and
terminations [5]. In addition, in ame atomizers, usage of fuel-rich molecule-forming agent. While selecting wavelength, it is impor-
ame provides excess C for the evaluation of CS diatomic mole- tant that selected wavelength should not have any spectral in-
cules. In graphite furnace atomizers, graphite interacts with sulfur, terferences because of absorption wavelengths caused by matrix
 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76 67

components. In the literature, it was mentioned that one of the low
sensitivity secondary lines of iron (258.045 nm) may cause spectral
interferences because of overlapping with 258.056 nm of CS line
[40]. In Table 4, the most used sulfur diatomic lines are listed with
possible spectral interferences between central pixel 25 pixel.
Simultaneous monitoring of different wavelengths is also
possible with software, which is expected to improve linear range
or a better limit of detection. However, it is important to be aware of
possible spectral interferences, especially spectral windows that
have various elemental lines. For example, Bechlin et al. [56]
investigated the summation of CS wavelengths 257.595 and
257.958 nm. Because 257.958 nm is narrower than 257.595 nm, the
use of more pixels increases the noise, and higher integrated areas
deteriorated the limit of detection for summed lines. Resano and
Flores [57] tried to combine six CS lines, namely 257.958, 257.850,
257.864, 257.908, 258.033, and 258.056 nm. In this case, improving
linearity was not feasible because their sensitivity varies only very
moderately (10e30%). Nevertheless, combining these lines
decreased the LOD to 3 ng, which was an improvement. In addition,
Zambrzycka and Godlewska-Zylkiewicz [58] summated
257.959 nm, 258.033 nm, and 258.055 nm (central pixels), and the
sensitivity of the measurements increased by a factor of 3, whereas
the LOD value was 2e5 times lower than that of the individual lines.
The sensitivity of measurements may be improved by increasing
the number of pixels used for detection. The important parameter
while selecting pixels is to be sure that there is no spectral over-
lapping between molecular absorbance and spectral interferences.
In many studies, different number of pixels is evaluated and opti-
mum number is selected [54,56,58].
4.2. Selection of sensitivity parameters
In AAS, same analyte may cause different atomization peaks
depending on (i) analyte's condition in solution (bound or free), (ii)
analyte's oxidation state, and (iii) analyte's form (organic or inor-
ganic). In MAS, an interaction balance occurs between analyte and
molecule-forming element in addition to the formation of atoms.
There are various studies [5,20,59] about sensitivity differences
ame atomizers for sulfur compounds. In these studies, the authors
observed that CS molecular absorption is independent from the
chemical form of sulfur in solution, but sensitivity is strongly
dependent on the specic sulfur form. They also tried various
chemical forms of sulfur standards to compare [H2SO4, (NH4)SO4,
KHSO4, Na2SO3, Na2S2O3, (NH4)2S] and found that (i) solutions
based on sulfate form resulted in same sensitivity, which are also
stable with the presence of HNO3, (ii) in the absence of acid, Na2SO3
and Na2S2O3 gave same sensitivity, but in acidic conditions, sensi-
tivity was enhanced, which could not be explained by the authors,
(iii) (NH4)2S in solution (acidic or not) has higher sensitivity than (i)
solutions. However, with the addition of H2O2 [1% (v/v)] to (NH4)2S,
which converts sulde to sulfate, sensitivity reduces. All these re-
sults demonstrate that CS absorption is dependent on chemical
forms of sulfur and the composition of standard solutions. In
addition, while sulde forms give better sensitivity, sulfate forms
are more stable, and sulfur forms in samples can be easily con-
verted to sulfate with some pretreatment. Therefore, the usage of
(NH4)SO4 is suggested by authors. However, it is important to have
knowledge about sulfur forms in sample as they would denitely
have different sensitivities in ame atomizer.
Similarly, in graphite atomizer, form of sulfur components,
which can be either organic or inorganic, becomes important.
While using this type of atomizers, samples and standards should
have similar sensitivities in each temperature, i.e., pyrolysis and
molecule formation curves and similar molecule formation proles,
i.e., time versus absorbance curve. Similar sensitivities can be ob-
tained by the usage of modiers to eliminate this disadvantage
because modiers stabilize different kinds of compounds during
prolonged periods.

Table 4
Commonly used sulfur diatomic lines with possible interferences. Information taken from Aspect CS 2.0.1.0 Software.

Diatomic Main line Element Wavelength Relative Diatomic Main line Element Wavelength Relative
molecule (nm) (nm) sensitivity (%) molecule (nm) (nm) sensitivity (%)

CS 257.595 Al 257.540 1.9 SnS 271.578 Fe 271.532 0.0033

Mn 257.551 0.0013 W 271.550 2.3
Dy 257.558 1.1 Nb 271.550 1.5
Co 257.573 0.029 Nb 271.569 3.1
Cr 257.590 0.0028 Lu 271.569 3.1
Gd 257.603 0.77 Co 271.599 0.00067
257.959 Cr 257.916 0.0091 Nb 271.610 5.9
Fe 257.927 0.00067 Cr 271.610 0.01
Zr 257.955 4.8 271.624 Nb 271.569 3.1
Ta 257.955 2.9 Lu 271.591 2.1
Fe 258.045 0.00053 Co 271.599 0.00067
258.033 Fe 258.007 0.00067 Nb 271.610 5.9
Tl 258.014 4.8 Cr 271.617 0.01
Ta 258.016 4 Dy 271.639 0.56
W 258.034 5.6 SH 323.658 Fe 323.622 0.031
Fe 258.045 0.00053 Mn 323.678 0.0012
W 258.049 28 Co 323.702 0.12
Eu 258.062 0.038 Fe 323.622 0.031
Ti 258.084 0.067 324.064 Tb 324.031 1.4
258.056 Fe 258.007 0.00067 Gd 324.112 12
Tl 258.014 4.8 327.990 Cu 327.981 0.00029
Ta 258.016 4 Gd 327.992 21
W 258.034 5.6 Sm 328.022 0.37
Er 258.035 0.13
Fe 258.045 0.00053
W 258.049 28
Eu 258.062 0.038
Ti 258.082 0.18
Co 258.084 0.067
Table 5

68
Literature summary for high-resolution continuum source ame molecular absorption spectrometry (HR CS FMAS) studies.

Sample Molecule Fuel Flame Standarda Calibration method Pretreatment LOD Ref
height

Wine CS Acetylene/Air 6-9 mm (NH4)SO4 Standard Addition 2% (v/v) hydrogen peroxide and 2% (v/v) 2.4 mg L
1 [5]
258.056 nm (3.8 L min
1/ NaSO3 Method nitric acid added to convert sulfur forms
(CP 1, 3 pixels) 17 L min
1) to sulfate
Cast iron CRMs CS Acetylene/Air 7 mm (NH4)SO4 Standard Addition 2 g of cast iron CRM heated with 25 mL 4.4 mg L
1 (257.593 nm) [20]
257.593 nm (3.8 L min
1/ H2SO4 Method 1:1 nitric acid. Subsequently, 10-mL 2.4 mg L
1 (258.056 nm)
(CP 1, 3 pixels) 17 L min
1) KSO4 HClO4 added and mixture heated till
NaSO3 fuming. Digestion solutions transferred
Na2S2O3 to volumetric ask and made up to
(NH4)2SO3 50 mL with water. Before analysis,
solutions were diluted by a factor 2.
Wine CS Acetylene/Air 6-9 mm (NH4)SO4 Linear Calibration A 7.5-mL wine sample acidied by 1.8 mg L
1 [59]
258.056 nm (3.8 L min
1/ NaSO3 adding 0.15-mL concentrated HCl and
(CP 1, 3 pixels) 17 L min
1) diluted with water till 15 mL.
Another 7.5-mL wine sample acidied

N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76

by adding 0.15-mL concentrated HCl
and oxidized free SO2 to sulfate with
0.15-mL mixed KI/I2 solution and
diluted with water till 15 mL.
Another 25-mL wine sample and 5-mL
concentrated HCl incubated in water
bath, and total SO2 removed by
bubbling with nitrogen gas ow and
diluted with water 50 mL.
Plants CS Acetylene/Air 8 mm (NH4)SO4 Linear Calibration Air-dried 0.5-mg sample weighed and 14 mg L
1 [75]
257.961 nm mineralized with 10-mL HNO3
gradually warming overnight. After
cooling, 3 mL of H2O2 and 10 mL of
HNO3 added, and
Fungicide and CS Acetylene/Air 7 mm (NH4)SO4 Linear Calibration 200-mg fungicide samples mineralized 15.1 mg L
1 (257.595 nm) [54]
Fertilizer Samples 257.595 nm (110 L h
1/ in 4-mL HNO3 and 1-mL HCl in with 22.4 mg L
1 (257.958 nm)
257.958 nm 521 L h
1) microwave digestion, 21.8 mg L
1 (258.056 nm)
258.056 nm 250-mg fertilizer samples dissolved in
(CP, 1 pixel) 50-mL water.
SH Acetylene/Air 7 mm (NH4)SO4 Linear Calibration 200-mg fungicide samples mineralized 2558.3 mg L
1 (323.658 nm) [54]
323.658 nm (110 L h
1/ in 4-mL HNO3 and 1-mL HCl in with 1502.8 mg L
1 (324.064 nm)
324.064 nm 521 L h
1) microwave digestion 955.8 mg L
1 (327.990 nm)
327.990 nm 250-mg fertilizer samples dissolved in
(CP, 1 pixel) 50-mL water
Coal CS Air/Acetylene 10 mm H2SO4 Linear Calibration 0.2-g dried samples dissolved by 100 mg L
1 [49]
258.056 nm (80 L h
1) microwave-assisted digestion using 10-
(CP 2, 5 pixels) mL HNO3
Petroleum products CS Air/Acetylene 9 mm Dibuthyl sulde Petroleum Products Products melted on dryer at 50e80 C, 21 mg L
1 [61]
258.056 nm (75 L h
1/70 L h
1) Ternonyl with known S dissolved in xylene in ratios 1:25 and
(CP 2, 5 pixels) Polysulde concentrations 1:50 m/v
Sulfuric acid
CS2
Medicinal plants and CS Air/Acetylene MgSO4$7H2O Linear Calibration 2000-g dried samples mineralized in 30.5 mg L
1 (summation of [56]
CRMs Summation of (120 L h
1) block digestor with 3.5-mL H2O2 and 257.595 257.958 nm, CP 2
257.595 10-mL HNO3 and tubes placed in block pixels)
257.958 nm digestor at 90 C for 2 h till solution
(CP 2, 5 pixels) evaporated to dryness. The residue is
taken up in water, ltered, and added
5 mL of 5000 mg L
1 Ti and completed
to 25 mL with water.
 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76 69

4.3. Optimization parameters of ame atomizers

[63]

[58]

Similar to all determinations with ame atomizers, ame

composition and observation height are critical factors. Until now,
only CS diatomic molecule was determined in ame atomizer. In
many studies, it is mostly emphasized that CS absorption only ap-
pears in extremely fuel-rich ame conditions. Because fuel-rich
ame provides excess free carbon (C) for the formation of CS and
the decomposition reaction of CS with excess oxygen (O) has a very
low activation energy (0.0e6.3 kJ mol
1) [60], CS formation can
10.9 mg L
1
1.2 mg L
1

easily occur in hot ame conditions. Nevertheless, to prevent

decomposition, atomic oxygen in the ame must be eliminated.
The main disadvantage of using fuel-rich ame is the formation of
unburned carbon particles, which tends to scatter the radiation of
Egg white: 1:1 dilution with 0.1 M NaCl

diluted to 10 mL with 0.2-mol L
1 HNO3

CRM: 0.5-g sample mineralized in 6-mL
concentrated HNO3 and 1 mL H2O2 and
microwave-assisted digestion using 7-

the continuum lamp. This effect was tested by Huang et al. [20] who
Water/Wine: acidication with HNO3,
Milk: dilution with 3 mL 0.1 M HCl

found out that transmittance degraded to 75% of its origin value.

0.4-g dried sample mineralized in

However, because the intensity of the lamp is high and sufcient

and background correction algorithms can correct unspecic ab-
sorption scattering, there is no inuence on analyte signal. In
degassed under vacuum

addition, because of relatively high temperature of this ame type,

disulde (S2) species cannot exist and cannot overlap with the
spectra [20].
As for the ame height, there is a specic window for CS signal.
mL HNO3

In lower zones of ame, combustion is incomplete and high con-

centration of oxygen can be found, which lowers the possibility of
formation and stability of CS molecule. For higher observation
heights, atmospheric oxygen can diffuse to the ame, which also
lowers the possibility of formation and stability of CS [20].
There are many studies for sulfur determination in ame at-
Linear Calibration

Linear Calibration

omizers, which are summarized in Table 5. In the rst paper, Huang

et al. determined total sulfur in wine samples [5] and then different
sulfur forms in wine matrix [59] from CS diatomic line at
258.056 nm by an air-acetylene ame. In this paper, sensitivity
differences of sulfur forms were found, and because wines have
different forms of sulfur, samples were pretreated with 2% (v/v)
hydrogen peroxide and 2% (v/v) nitric acid. In addition, decreasing
effect of ethanol on the sensitivity of CS was found for the wine
DL-cysteine

(NH4)2SO4
L-cysteine

samples that contain 12e13% (v/v) ethanol. The method has been
Na2SO4

Na2SO3
H2SO4

H2SO4

proved to be reliable and robust, and no serious spectral and matrix

Na2S

interference were observed in the presence of up to 5% (v/v) nitric,

hydrochloric, perchloric, or hydrouoric acids and up to
2000 mg L
1 solutions of Al, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, and Ni.
13 mm

8 mm

Only matrix interference was found for Pb at concentrations higher

than 200 mg L
1, which is caused by the precipitation of lead sul-
fate. In the second paper, using this information, total sulfur, free
SO2, and sulfate were determined. In addition, the effect of HCl and
HNO3 on CS absorption was investigated. At high pH values, sen-
Air/Acetylene

Air/Acetylene

sitivities were at the same level, but small amounts of acid led to a
(120 L h
1)
(90 L h
1)

strong increase of CS absorption with sulte standard, whereas

sulfate standard's sensitivity remained unchanged. Further addi-
tion of acid up to 5% did not inuence CS sensitivity, which was
Underlined standard used for quantication.

explained by the efcient transport of gaseous SO2 during sample

(CP 2, 5 pixels)

(CP 1, 3 pixels)

nebulization for ionic forms of sulfur.

The same group [20] determined sulfur concentration in cast
258.056 nm

258.055 nm

iron standard reference materials (EURONORM ZRM 428-2 and

EURONORM ZRM 484-1) from CS diatomic line at 257.959 nm by
CS

air-acetylene ame in 2006. Various chemical forms of sulfur

standards were compared, and as a result, usage of (NH4)SO4 is
suggested. For spectral interferences, 1% (m/v) metallic salt solu-
Food Samples and

tions of Ag, Al, Bi, Ca, Co, Cr, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, Pb, Sn, and
Food/Beverage

Zn were checked. Studied lines were sufciently separated from CS

samples

line (258.056 nm), except the weak Fe line (258.045 nm). The Fe
CRMs

line interfered spectrally, but fortunately, this line was weak. For
chemical interferences, Al, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb,
a

and some inorganic acids [HNO3, HCl, HF, HClO4 up to 5% (v/v)]

70 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76
were studied, and there was no chemical interference, except Pb,
which forms lead sulfate in higher concentrations (200 mg L
1) and
reduced the CS absorption. Because cast iron matrix had a high
concentration of Fe, 258.056 nm for CS line could not be used, and
therefore, 257.959 nm was selected instead. Because of the low
concentration of sulfur, further dilution of sample was not possible.
In addition, the dilution of sample would cause change of matrix of
sample, which would affect the aspiration rate of the nebulizer. To
overcome this physical inuence, standard addition method was
applied.
Kowalewska [61] also used CS line at 258.056 nm (CP 2) to
determine sulfur concentrations in various petroleum products.
Samples were prepared in xylene solution. Volatile sulfur com-
pounds, such as CS2, could not be determined using the ame MAS
because of high and variable efciency of evaporation into the
observation area (i.e., overestimated results). Standardization with
dibutyl sulde failed with ame analysis, so petroleum products
with known sulfur concentrations are recommended.
Virgilio et al. [54] used CS lines (257.595, 257.958, and
258.056 nm) and SH lines (323.658, 324.064, and 327.990 nm) to
determine total sulfur concentrations in agricultural samples. The
inuence of potential interfering elements was tested, and the ef-
fect of Ca, Cu, Fe, K, Mn, Na, P, Si, and Zn was signicantly found for
the line 323.658 nm. For 257.958, 258.056, and 324.064 nm lines,
there was no interference. Among the latter, 324.064 nm suffered
from poor precision. Overall, CS lines showed better sensitivity than
SH lines, but the precision of CS lines was lower. After all the
evaluations, 257.595, 257.958, and 258.056 nm (integration of 1
pixel) were selected as optimum lines for determination. Finally,
sulfur concentrations in some fungicide samples were determined
using these three different lines. The results were compared with
gravimetric methods and found to have no signicant difference.
Baysal and Akman [49] used CS line at 258.056 nm to determine
total sulfur concentrations in coal samples by air-acetylene ame
using H2SO4 as a calibration reagent for linear calibration method.
For preparing samples, open digestion procedures were compared
with microwave digestion procedure, and it was found out that
open digestion procedure lead to lower accuracies, possibly
because of analyte losses.
Bechlin et al. [56] determined sulfur concentrations of medical
plants at CS lines 249.773, 257.595, and 257.958 nm by comparing
the number of pixels and also comparing results with the sum-
mation of lines. Lower LOD values were obtained for the line
257.595 nm, independent of the number of pixels. Summation of
absorbance improved LOD values for 1 and 3 pixels in a factor of
square root of n, where n is the number of lines summed as
mentioned in a work by Heitmann [62]. Higher integration areas
deteriorate the LOD of summed lines when some lines are narrower
than others, i.e., 257.958 nm. In this situation, using more pixels
increases the noise. In conclusion, the summation of absorbances
for CS lines (257.595 and 257.958 nm) furnished a LOD only 10%
lower than that obtained for the line 257.595 nm using 5 pixels.
Zambrzycka and Godlewska-Zylkiewicz [58] determined sulfur
in some food and beverage samples at 258.055 nm (integration of 3
pixels) by air-acetylene ame using DL-cysteine as a calibration
reagent. Before selecting the wavelength (257.959, 258.033, and
258.055 nm), their summation absorbances were compared. In-
uence of nitric acid on sulfur standard was also investigated. In the
presence of nitric acid, a rapid increase of absorbance for sulte and
sulde was found. To avoid differences in the formation of CS
molecule from standards and digested samples, standards were
also prepared in HNO3. Highest sensitivity of calibration graphs was
obtained using solutions containing sulte; however, because sul-
tes in samples might be converted to sulfates in acidic conditions,
this standard is not recommended. In addition, sodium sulte in
acidic solution converted to volatile H2S, which was continuously
evaporated from solution during storage of samples. The absor-
bance of organic standards was constant in H2O2, ethanol, HCO3,
and NaCl, and the lowest inuence of Pb2, Mg2, and Ca2 was
observed on the signal of DL-cysteine, which was, therefore,
selected as calibration reagent.
Ozbek and Baysal [63] used CS line at 258.056 nm to determine
total sulfur concentrations in various fresh and dried food samples
by air-acetylene ame using H2SO4 as a calibrant for the linear
calibration method. Samples were rst dried and then digested in
microwave. Stability of samples digested with only HNO3 was
better than those digested by HNO3 H2O2.
4.4. Optimization parameters of graphite furnace atomizers
To measure the diatomic molecule absorption in graphite
furnace atomizer, the highest density of molecules in atomization
stage needs to be created. In addition, the concentration of
molecule-forming reagent and optimum molecule-forming tem-
perature play a critical role. Optimum molecule-forming tempera-
ture should be high enough to create the molecule and should be
low enough to not remove the molecule too rapidly from the ab-
sorption volume because of increased diffusion [38]. Sulfur stabi-
lization can be obtained by using chemical modiers, which would
allow the usage of high pyrolysis temperature to remove the ma-
jority of matrix and destroy original molecules containing sulfur
without losing the analyte [64]. In this way, it would be possible to
use the pyrolysis temperatures high enough to remove most of
matrix components, but also analytical response may be normal-
ized regardless of the chemical form in which sulfur is introduced
[57]. Moreover, heating rate is an important parameter, as
mentioned by Gunduz and Akman [65].
Matrix effect or interferences can be removed or decreased by
the modiers in atomic spectrometry. Various types of modiers,
i.e., Ca, Mg, and Pd, were investigated in the literature by the sci-
entists. For these purposes, different kinds of modiers were
investigated in different studies: Ca modier [40], Pd/Mg modier
[61], PdCl2 nanoparticles [66], Pd nanoparticles [57], Pd modier
[39,53,67], and Pd/citric acid mixture as modier [65,68]. In some
papers, usage of Ca is promoted [69], but its use as the modier
deteriorates graphite furnace and tubes signicantly, which is an
unwanted effect [40]. Universal modier Pd is used mainly for
sulfur analysis, but the choice of its chemical form is also critical.
Nitrate solution can stabilize inorganic species, but it is not efcient
for volatile organic ones. For this purpose, Pd can be reduced
because the metallic form of Pd is believed to be the most active
one. This reduction can be achieved either thermally or by the
addition of citric acid as reductant. Citric acid addition also releases
active carbon, which is necessary for CS evaluation. Finally, the
addition of Pd nanoparticles is another approach to overcome
matrix effect and interferences. Although Pd nitrate solutions are
known to migrate toward the edges of platform, Pd nanoparticles
(Pd NPs) tend to have a homogenous distribution on the platform
[57].
For graphite furnace atomizers, in general, pyrolytically coated
graphite tubes are used. These types of tubes are necessary,
otherwise graphite interacts with sulfur, which evolves volatile CS2
and thus reduces the analyte. Without coating, the signal intensity
is only about 20e30% of the coated value [70]. Ferreira et al. [40]
tried tubes without pyrolytic coating (using platforms coated WC)
to promote the formation of CS because of a gasesolid reaction with
the tube surface and reduce the oxygen content in the gas phase;
however, no signicant increase in the absorbance of CS was
observed. In addition, Baumbach et al. [70] investigated the mole-
cule formation with integrated platform graphite furnaces and
 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76
found that repeatability of measurements failed and the signal in-
tensity minimized by one-third. Although the delay of heating in
graphite tube platform is an advantage for atom formation in AAS
analysis, the analyte should be immediately in vapor phase for
molecule formation. Direct formation of diatomic molecules in the
evaporation step was proved by Gilmutdinov et al. through some
experiments [71]. However, Huber et al. [64] found no signicant
difference in the signals with or without platform tube. Further-
more, Ferreira et al. [40] suggested that the use of carbide forming
elements could prevent sulfur losses because of the formation of
CS2 molecule. However, the mechanism of refractory carbide-
forming elements increasing CS sensitivity cannot be understood
yet; however, because the classical procedure of synthesizing CS2 is
by conducting sulfur vapor over charcoal at 800e1000 C, sulfur in
graphite furnace can also intercalate and form volatile CS2 [40]. As a
conclusion, by coating furnace/platform with refractory elements,
contact of sulfur with carbon would be reduced, which would
eventually increase the absorbance.
Different approaches were used in different papers to prevent
the evolution of CS2 such as using low pyrolysis temperature [72]
and deposition of Pd [53], Zr [69,70], W [40,65], Ru [57,68,73],
and Ir [39,67] on graphite furnace. The addition of methane in
argon mixture [69] in pyrolysis stage was found to have an
increasing effect on CS2 formation by Heitmann et al.
Under the circumstances mentioned above, some papers for the
determination of sulfur by graphite furnace MAS (GF MAS) are
listed and summarized in Table 6.
Ferreira et al. [40] determined sulfur in biological samples at
258.033 nm with solid sampling. W and Zr were assessed as per-
manent modiers. Although Zr permanent modier gave the best
sensitivity, W showed long-term stability. Moreover, Ca, Mg, and Pd
were tried as modiers to improve sensitivity, and best sensitivities
were obtained with Ca. However, tubes and graphite furnace
deteriorated signicantly with Ca, and the integrated absorbances
were not proportional to certied values. Sulfuric acid, ammonium
sulfate, magnesium sulfate, sodium sulte, sulfanilic acid, sulfa-
nilamide, and thiourea were tried as a standard solution. Ammo-
nium sulfate and H2SO4 could not be stabilized at all, while
magnesium sulfate and sodium sulte stabilized at pyrolysis tem-
perature around 600 C, which was unsatisfactory compared with
Certied Reference Material (CRM) temperatures. Because CRMs
have carbon in structure, inorganic standards might be responsible
for the low sensitivity and thermal instability. Thus, organic stan-
dards were investigated, and it was found that thiourea provides
satisfactory results to determine sulfur concentrations in biological
CRMs.
In the same study, Kowalewska [61] used graphite furnace to
determine CS line at 258.056 nm (CP 2). As ame atomizer, for
volatile petroleum products, this method could not be applicable
because stable and volatile sulfur compounds could be completely
volatilized before measurement without destroying the original
bond and CS formation. For heavier petroleum products and crude
oil, Pd was used as modier to prevent the loss of volatile sulfur
forms. This modier also unied the behavior of various sulfur
compounds and facilitated the formation of CS. Finally, the mixed
Pd Mg modier turned out to be the most efcient one for this
work.
Resano and Florez [57] determined sulfur in various matrixes
with solid sampling by using CS line at 257.958 nm (integration of 3
pixels). Ru was used as a permanent modier, whereas Pd NPs were
used as modiers. Potential of simultaneous determination of
various lines were investigated, and it was concluded that it had a
decreasing effect on LOD. Different kinds of solid samples have
different kinds of temporal proles, which was an expected
outcome for solid sampling technique. For steel samples, sulfur
71
signal is delayed, and samples left deposits on platform. After the
analysis of 40 samples, the platform should be replaced to avoid the
loss of sensitivity.
Mior et al. [73] determined sulfur in coal samples by solid
sampling using CS line at 258.033 nm (integration of 3 pixels). In
the study, Ru was used as a permanent modier, but using Ru
with Pd/Mg modier together caused a negative effect on sensi-
tivity and stability. Ammonium sulfate, magnesium sulfate, thio-
urea, and L-cysteine were used as calibration standards. Although
ammonium sulfate and thiourea did not produce any spectrum,
magnesium sulfate and L-cysteine were found to be useful.
Because their thermal behaviors are different from each other and
coal samples are organic, L-cysteine was selected. In addition,
while optimizing vaporization and pyrolysis temperatures, time-
resolved absorbance signals showed double peaks in vapor-
ization stage, which suggests the presence of two sulfur species of
substantially different volatilities (rst one is organically bound to
sulfur, and second one is much more stable and inorganically
bound to sulfur).
Nakadi et al. [72] determined sulfur concentrations in coal by
slurry sampling using CS line at 257.592 nm by evaluating peak
height. Samples were prepared in 5% (v/v) nitric acid solution
mixed with 0.04% (w/v) Triton X-100. In the study, low pyrolysis
temperature (300 C) was used to avoid the use of any modier.
Ozbek and Akman [39] used 258.056-nm molecular absorption
line of CS (integration of 3 pixels) to determine total sulfur in food
samples by solid sampling. Ir-coated platforms with Pd modiers
were used, and calibration curve was evaluated with Na2S. Effect of
sample quantity and homogeneity of samples were investigated.
Nakadi et al. [66] determined sulfur concentrations in diesel
samples from diatomic CS line at 258.056 nm (integration of 3
pixels) with the help of palladium nanoparticles. Different surfac-
tants (Triton-X 100 and Triton X-114) and alcohols (ethanol, n-
propanol, isopropanol, and n-butanol) were studied with time us-
ing the highest sample/solution volume ratio possible. Triton-X 114
provided an emulsion that was stable for hours, but this mixture
was not appropriate for analysis because its high organic content
generates smoke inside the graphite furnace. All alcohol emulsions
behaved the same, so ethanol was selected as the least toxic one. Pd
NPs and PdCl2 NPs were tried as modiers, and PdCl2 NPs was
selected because it affords slightly better signal. Three standards
were tested (thiourea, sodium sulfate, and 2-mercaptoethanol)
with Pd NPs, and it was found out that time-resolved peaks
behaved the same way virtually, which proves Pd NPs could sta-
bilize them efciently. Thiourea was chosen because of its low
RSDs. For low-sulfur-containing diesel samples, alcohol emulsion
method was not applicable because of its high LOD. For this kind of
samples, direct injection with lower pyrolysis temperature was
applied. Sample injection was performed manually on solid sam-
pling platform instead of liquid auto-sampler, which increased RSD
values, but this had a negative effect on the analysis time.
Gunduz and Akman [65] summated two rotational lines of CS
molecule 257.959 and 258.056 nm (3 pixels 3 pixels) to deter-
mine sulfur concentrations in some nuts and dried fruits. Thiourea
was used for linear calibration because its thermal behavior (py-
rolysis and volatilization curves) is more similar to CRMs and
samples. Effect of heating rate on sensitivity was investigated as
well, and 3000 C s
1 was selected. Simultaneous evaluation of
absorbances, i.e., summation of two different peaks of CS molecule,
increases both the sensitivity and standard deviation, which have
opposite effects on the LOD. If the increase in sensitivity were more
pronounced, then LOD would be lowered. Finally, sulfur concen-
trations in some nuts and dried fruit samples were determined by
wolfram-coated platform/graphite tube with Pd/citric acid
modier.
Table 6

72
Literature research for high-resolution continuum source graphite furnace molecular absorption spectrometry (HR CS GF MAS) studied.

Sample Molecule Pyrolysis Molecule Analysis Standarda Calibration Pretreatment LOD Notes Ref.
temperature formation time (s) method
( C) temperature
( C)

Spinach CRM, Peach CS 700 2400 58 (NH4)2SO4 Linear 0.15e0.2 g were 2.3 ng Zr-coated with Ca [69]
leaves CRM 258.056 nm digested with 2 mL modier Ar-methane as
Integration of 3 pixels HNO3 and 2 mL H2O2, alternate gas
then made up to 15 mL
with water
Biological samples CS 900 2500 50 Thiourea Linear Solid Sampling 15 ng W permanent modier [40]
258.033 nm H2SO4 with Pd modier
Integration of (CP 1) 3 (NH4)2SO4
pixels MgSO4
Na2SO4
Sulfanilic acid
Sulfanilamide

N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76

Petroleum products CS 400 2400 92 Dibuthyl sulde Petroleum Products Products melted on 14 ng Pd Mg Modier [61]
and CRMs 258.056 nm Ternonyl Polysulde with known S dryer at 50e80 C,
Integration of (CP 2) 5 CS2 concentrations dissolved in xylene in
pixels Sulfuric acid ratio 1/25, 1/50 m/v
Biological, petroleum CS 800 2400 45 Na2SO4 Linear Solid Sampling 9 ng Ru permanent modier [57]
coke, polyethylene, 257.958 nm Na2SO3 3 ng with Pd NPs
steel CRM Integration of (CP 1) 3 Thiourea (combination
pixels 3-mercaptionic acid of 6 lines)
Water SnS 500 1850 74 Na2SO4 Linear No preparation 0.16 ng Zr-deposited graphite [70]
271.578 nm tube (no platform)
Integration of (CP 2) 5
pixels
Coal CS 300 2500 59 Ammonium sulfate Linear Slurry Sampling 0.15 ngb Low pyrolysis [72]
257.592 nm temperature
Peak height
Coal and CRMs CS 500 2200 39 L-cysteine Linear Solid Sampling 30 ng Ru-deposited graphite [73]
258.033 nm tube/platform
Integration of (CP 1) 3
pixels
Food and CRMs CS 1000 2400 56 Na2S Linear Solid Sampling 3.5 ng Ir-coated platform/tube [39]
258.056 nm with Pd modier
Integration of (CP 1) 3
pixels
PM 2.5 air particulate CS 850 2400 34 H2SO4 Linear 0.1 g loaded lter pieces 10 ngb e [74]
matters 258.056 nm were precisely weighed
Integration of (CP 1) 3 and placed into
pixels polyethylene tubes,
then
agitated using 5 mL
with water or 5 M
HNO3 for 30 min.
Coal and CRMs SnS 550 2100 59 Thiourea Linear/solid Solid Sampling/0.5-g 10 ng Ir-deposited graphite [67]
271.578 nm Na2SO4 standardization sample mineralized in tube/platform with Pd
Integration of (CP 2) 5 cysteine microwave digestion modier
pixels with 3-mL H2O2, 8-mL
HNO3 and 1-mL HF,
neutralized with 10-mL
H3BO4.
 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76 73

The same authors [68] determined sulfur concentrations in

[65]

[66]

[68]

[64]

[53]
various vegetables by molecular absorption of CS molecule at
258.056 nm (3 pixels) by solid sampling. In this work, Ru-coated
Pd citric acid modier

Ru-deposited graphite

Pd-deposited graphite
W-deposited graphite

platform and graphite tube with Pd/citric acid modier were used.

Ir-deposited graphite
with Pd citric acid
PdCl2 nanoparticles
tube/platform with

tube with Pd Mg
tube with platform
Huber et al. [64] monitored diatomic CS line at 258.056 nm
(integration of 3 pixels) to determine the best chemical modier for
the determination of sulfur concentration in diesel fuel samples.

modier

modier
After trying various chemical modiers to inject with sample (Pd,
Mg, Pd Mg, Ca) and permanent modiers (Zr, Ir, and Ru), which

tube
were deposited to graphite furnace, Ir (permanent modier) with
Pd Mg mixture was selected as a modier. Diesel samples were
samples 7.2 ng
of 258.959
258.056 nm)
(summation

diluted with propan-1-ol. For high concentration samples, there is

for direct
21.6 ngb

some limitation in the mass of sulfur that can be stabilized.

3.6 ng

5.8 ng
7.5 ng
diesel

Accordingly, for samples with unknown sulfur content, dilution of

sample was advised. If there is an absence of CS signal, concen-
tration could be gradually increased.
dissolved in n-propanol
0.125 kg L
1 of sample

MIBK, addition of Sn2

mixture of H2O2:HNO3

100 mL of diesel mixed

alcohol/water solution

Dilution with xylene,

Ozbek and Baysal [74] used CS diatomic line at 258.056 nm (3

mineralized in 7-mL

with 6-mL 50% (v/v)

0.5-g dried samples

(5:2) by microwave

addition of water,

pixels) to determine sulfur concentration in PM 2.5 air particulate

digestion system

Solid Sampling

in propan-1-ol

matters. Approximately 0.1-g-loaded lter pieces were precisely

weighed and placed into polyethylene tubes and then agitated
using 5-mL distilled water or 5 M HNO3 solution for 30 min. The
extracts were ltered using cellulose nitrate syringe lters
(0.45 mm) and then analyzed by graphite furnace HR CS AAS.
Baumbach et al. [70] used SnS diatomic molecule at 271.578 nm
(integration of 5 pixels) for sulfur determination in water samples.
Authors rst tried AlS, BaS, InS, and SnS diatomic molecules from
Parvinen et al. [42] and AlS, AsS, BaS, BeS, CaS, CrS, CuS, GeS, MgS,
SeS, SiS, SnS, and TiS from PLASUS Specline Database and nally
Linear

Linear

Linear

Linear

Linear

selected SnS because of it showed the highest absorbance. Sodium

sulfate was used for calibration. The presence of Al, Ca, Cd, Cr, Cu,
Mg, Na, Pb, and Zr showed no interference, while Co, Fe, K, Mn, and
2-mercaptoethanol

Ni generated stable sulfur compounds and decreased the SnS signal

Sodium sulfate;

by 10e15%. Ni showed the strongest interelement effect because it

Thioacetamide

creates thermally stable NiS element. There was no spectral inter-

L-cysteine

L-cysteine
Thiourea;
Thiourea

Thiourea

ference around 271.578 nm. Finally, according to parameters above,

NH3SO3
Na2SO4

Na2SO4
K2S2O7

sulfur concentrations in different waters were determined.

The same group [67] used SnS molecule at 271.578 nm (inte-
gration of 5 pixels) to determine sulfur in coal samples by solid
sampling. They compared the solid sampling results with micro-
NGc

85

47

99

71

wave digestion results and found no signicant difference.

Cadorim et al. [53] used SnS molecule at 271.624 nm (integra-
samples: 2500

tion of 5 pixels) to determine sulfur in crude oil samples. High

for direct

viscosity of samples forced them to perform microemulsion sample

diesel
2400,
2200

2400

2500

2000

preparation; dilution with xylene; and addition of HNO3, water, and

MIBK, and Sn2 was prepared in n-propanol. Pd was selected as a
permanent modier for determination. Na2SO4 was used for cali-
samples: 130

bration, but its behavior was expected to be different from the

for direct

microemulsion of organic compound. In experiments, their be-

diesel

1000

1100
110,
800

600

haviors were found to be similar, but there was a very notable

difference in sensitivity, which could not be explained. At 2000 C
258.959 258.056 nm

Calculations based on 10-mL sample injections.

vaporization temperature, the absorbances and the temperature

Integration of 3 pixels

Integration of 3 pixels

Integration of 5 pixels
Integration of (CP 1)

Underlined standard used for quantication.

selected for molecule formation were found to be the same. Finally,

sulfur concentration in microemulsions of crude oil was
3 3 pixels

258.056 nm

258.056 nm

258.056 nm

271.624 nm

determined.

5. Outlook
SnS
CS

CS

CS

CS

Many industries need various forms of sulfur on a diverse array

Nuts-Dried Fruits and

Vegetables and CRMs

of application area. These applications require sulfur de-

terminations in elds of environmental (water, soil, and air), food
NG: not given.
Diesel and CRM

(food safety and nutritional labeling), pharmaceutical (drug

development and quality control), petrochemical (petroleum
Crude Oil
CRMs

rening and lubricants and oils), chemical/industrial (quality con-

Diesel

trol/product testing), geochemical/mining (exploration and

a
b
c

research), biomonitoring (biological uids), agriculture (soil

74 N. Ozbek, A. Baysal / Trends in Analytical Chemistry 88 (2017) 62e76

properties and fertilizers), semiconductor (wafers of high-purity

chemicals), nuclear energy, renewable energy (biofuels and solar
panels), and nanomaterials. These wide ranges of applications
demonstrate the importance of sulfur element. Therefore, the
determination of such an important element is under focus.
In addition, one of the most signicant advances, in the last de-
cades, is the introduction of high-resolution continuum source
atomic absorption spectrometers in atomic spectrometry and the
development of the continuum source. These improvements made
the determination of the nonmetals by atomic spectrometry
possible. For these purposes, scientic articles (indexed in Web of
Science between 2005 and 2016) that included the studies of sulfur
determination by HR CS AAS were evaluated in this review. This
instrumentation became commercially available in 2003, and at
rst, it was equipped with ame atomizer. Then, in 2007, the in-
Fig. 4. Number of publications that have reported the use of determination of sulfur by
strument was equipped with graphite furnace because of the great
high-resolution continuum source atomic absorption spectrometry during the last 10
effort by Becker-Ross and Welz [37]. The characteristic parameters years.
in these studies were evaluated by their molecule formation, at- Source: ISI Web of Science.
omization type, matrix type, and so on. In general, most of these
articles used the CS molecule formation by ame atomization. Dis-
tribution of these articles is in the food, petrochemical, geochemical/
mining, biological, agricultural, and environmental elds (Fig. 3).
High percentage of the investigated matrices belongs to food,
petrochemical, and geochemical/mining. The application of HR CS
AAS for sulfur determination includes pharmaceutical, chemical/
industrial, semiconductor, energy, and nanomaterial elds, but
there is no published article in these elds in the last 10 years.
As can be seen in Fig. 4, 23 articles were published during the
last 10 years using HR CS AAS in the journals, which were indexed
in Web of Science. During the period between 2010 and 2016, the
number of published articles has increased because of the interest
of different research groups with the development of high-
resolution graphite furnace AAS.
Increase in the number of the published articles has also lead to
Fig. 5. Citations in each year.
the signicant increase in the citations, especially during
2013e2015 (Fig. 5). Increase of the citation during these years is a
result of the development of the graphite furnace HR CS AAS, and
especially more citations were obtained in solid sampling articles. restricted chemicals. Although especially ICP-based techniques give
Tables 1, 5 and 6 summarize some properties of the different much better technical results, there are some drawbacks, such as
techniques such as ICP MS, ICP OES or tandem ICP MS techniques, high cost, matrix effect, polyatomic interferences, extra sample
and HR CS AAS for the determination of sulfur. Overall, it is difcult preparation steps, and technical background requirement. In
to point out which one is more advantageous. This decision de- addition, important parameters for the analytical techniques
pends on instrumental innovation, environmental and health including sensitivity, precision, and accuracy depend on some
impact studies, and the determination of legislation on the critical factors for ICP-based determinations; one of these impor-
tant factors is interference of the polyatomic ions. Several sample
preparation and introduction strategies have been proposed to
overcome this limitation. Thus, these strategies are mostly depen-
dent on instrumental modications. These drawbacks cause
complexity and extra cost for ICP-based techniques. On the con-
trary, HR CS AAS is a cost-effective method with easy instrumen-
tation and sample preparation, which is also free from
interferences. In addition, the LODs values are close to those of the
ICP-based techniques without any complicated sample preparation
or introduction methods. Moreover, sulfur is a ubiquitous element
present in many biological molecules, but there is no publication
for its determination using HR CS AAS. Therefore, selective detec-
tion or identication of sulfur forms that are determined by HR CS
AAS should be improved in the future studies.

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