Available online at www.sciencedirect.

com

Fuel 87 (2008) 10071013

www.fuelrst.com

Review article

Determination of sulfur compounds in gasoline using mercury

lm electrode by square wave voltammetry
Diana Maria Seram, Nelson Ramos Stradiotto

UNESP, Instituto de Qumica, Departamento de Qumica Analtica, Araraquara SP, Brazil

Received 25 February 2007; received in revised form 2 July 2007; accepted 12 July 2007
Available online 7 August 2007

Abstract
A sensitive method based on square wave voltammetry is described for the quantitative determination of elemental sulfur, disulde
and mercaptan in gasoline using a mercury lm electrode. These sulfur compounds can be quantied by direct dissolution of gasoline in a
supporting electrolyte followed by subsequent voltammetric measurement. The supporting electrolyte is 1.4 mol L1 sodium acetate and
2% acetic acid in methanol. Chemical and optimum operational conditions for the formation of the mercury lm were analyzed in this
study. The values obtained were a 4.3 lm thickness for the mercury lm, a 1000 rpm rotation frequency, 0.9 V applied potential and
600 s depositing time. Voltammetric measurements were obtained using square wave voltammetry with detection limits of the 3.0 109,
1.6 107 and 4.9 107 mol L1 for elemental sulfur, disulde and mercaptan, respectively.
 2007 Elsevier Ltd. All rights reserved.
Keywords: Sulfur compounds; Square wave voltammetry; Mercury lm electrode; Gasoline

Contents
1.
2.

3.

4.

5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Reagents and apparatus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Preparation of the MFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Preparation of copper column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5. Elemental sulfur, mercaptan and disulfide analysis in commercial samples of gasoline . . . . . . . . . . . . . . . . . .
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Formation of the mercury film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analytical performance of the procedure development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Analysis of gasoline samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Recovery of sulfur compounds in gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author. Tel.: +55 16 3301 6621; fax: +55 16 3322 7932.
E-mail address: nrstradi@iq.unesp.br (N.R. Stradiotto).

0016-2361/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.07.012

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

1008
1009
1009
1009
1009
1009
1009
1009
1009
1011
1011
1012
1012
1012
1012

1008

D.M. Seram, N.R. Stradiotto / Fuel 87 (2008) 10071013

1. Introduction
Due to the importance of sulfur in chemical, biological
and industrial areas, sulfur compounds have been extensively studied for many years [15], especially the determination of sulfur and its compounds in drugs, cosmetics,
foodstu, and petroleum products [69].
Sulfur has been the most abundant element in petroleum
after carbon and hydrogen for many years [10]. Nowadays,
in the case of the products resulting from the degradation
of organisms, oxygen and nitrogen are more abundant
than sulfur. It has been demonstrated that sulfur penetrates
into organic matter before crude oil is extracted and also
after the sedimentation process [11]. For a long period,
reducing bacteria in sediments have made changes in sulfate salts and have altered the formation of sulfur reducing
compounds such as H2S, S0, sulte, mercaptan and polysulde. In other words, these sulfur species are produced
by anaerobic bacterial reduction of sedimentary sulfate
deposits (mainly anhydrite or gypsum). The anaerobic bacteria consume sulfur instead of O2 as a source of energy
and a hydrogen acceptor to produce these sulfur compounds [12]. Apparently the reactions of these sulfur species and the formation of CS bonds cause the
occurrence of organosulfur compounds in petroleum derivatives. In order to properly remove sulfur from petroleum
and its derivatives, such as LPG, naphtha, gasoline, kerosene, gas oil and lubricants, it is necessary to appropriately
design oil facilities and develop a methodology to determine sulfur compounds especially in quality-control units.
Because various metals can suer the corrosive eect of
the sulfur compounds remaining after the rening of petroleum, it is interesting to have analytical methods to detect
and determine the most common sulfur compounds in
the rening industry. Several methods for the determination of sulfur compounds have been reported, including
colorimetric [13], titration [14], chromatographic [15], iodimetric [16,17] and X-ray uorescence spectrometry [18,19].
These methods are accurate and sensitive for the determination of elemental sulfur and mercaptan, but they are
time-consuming and tedious. In contrast to these methods,
electrochemical procedures are highly promising for
obtaining high sensitivity at good speed, low cost and a
low detection limit.
The general application of the electrochemical methods
for the analysis of sulfur compounds include polarography
to determine inorganic and organic compounds in petrochemical analysis [2022]. Usually, the polarographic
methods have been applied to the determination of only
one kind of sulfur compound, using solvents such as methanol and pyridine. Some works targeting the determination
of total sulfur, hydrogen sulde, elemental sulfur [23],
organic sulfur compounds and elemental sulfur [24] in oil
fractions have been reported. On the other hand, elemental
sulfur in fuels [25] and mercaptan sulfur in synthetic samples [26] have been determined using dierential pulse
polarography.

Kashiki and Ishida [27] accomplished the study of the

determination of mercaptan, disulde and elemental sulfur
in petroleum naphtha using square-wave polarography
implementing a dropping mercury electrode.
Chemically modied electrode also have been used for
determination of sulfur compounds in pharmaceutical formulations using boron doped diamond electrode [28],
determination of sulte in sugar using aluminum electrode
modied by nickel pentacyanonitrosylferrate lm [29] as
well as the analysis of sulde in cigarette smoke using
chemically modied screen-printed electrode [30].
An important drawback to electroanalytical techniques
is often attributed to the frequent necessity of using a hanging mercury drop electrode (HMDE), but its use has been
limited to analytical procedures due to the hazardous
eects of mercury. However, some molecules such as those
of the sulfur-compound class for example are electroactive
on a mercury surface, thus requiring the use of mercury
and the consequent risk of contamination. Having the
main objective of a avoiding the use of mercury in such
analysis, several modications of electrode surfaces have
been proposed. Due to this problem, allied to the highly
toxic nature of mercury, the research for new simple electrochemical electrodes for analysis and study of sulfur
compounds in fuel as well as other organic and inorganic
compounds is necessary. In this context, the mercury lm
deposited on a glassy-carbon electrode is a convenient electrode surface because it is practically non-toxic, easily prepared and is simple to regenerate electrochemically or
manually.
Chemical modication of electrode surfaces to carry out
mechanical or electrochemical analysis has several advantages in terms of selectivity, sensitivity and eciency for
the determination of a species using electroanalytical techniques [3133], including metal analysis of petroleum
derived from fossil fuels [34,35].
In this context, a successful electrode for analysis is a
mercury-lm electrode (MFE) comprising a thin layer of
mercury salt electrodeposited on a conventional solid and
an inert surface such as glassy carbon. This kind of electrode has experimental advantages such as high surface
area/volume ratio, resulting in a higher concentration of
amalgam during the deposition step, which increases the
sensitivity. Additionally, MFE has a high mechanical resistance, being stable under vigorously stirring or coupled
with ow systems [3638]. This feature increases their
applicability.
Several works have been reported in the literature using
the mercury-lm electrode, among them are works which
undertake the determination of pollutants such as the pesticide atrazine in soil and water [39] and the determination
of sulte in food using a sulte-oxidase biosensor-based
glassy-carbon electrode coated with a thin mercury lm
[40] as well as the simultaneous determination of zinc, copper, lead and cadmium in fuel ethanol [41].
Despite the importance of quality control for sulfur
compounds in fuel, the literature contains no reports of

D.M. Seram, N.R. Stradiotto / Fuel 87 (2008) 10071013

studies of these compounds using the MFE. So, the aim of

this work was to develop an electrochemical method to
determine disulde, mercaptan and elemental sulfur in gasoline based on square-wave voltammetry using a mercurylm electrode.

1009

smaller that 63 lm. However, a previous treatment of the

copper was necessary to activate its surface with successive
washes of the powder copper with the following solvents:
nitric acid 10%, distilled water, ethyl alcohol, acetone, ethyl
ether. Soon after this, the copper was ltered and carried to
a dessecator under a vacuum for drying.

2. Experimental
2.4. Procedure
2.1. Reagents and apparatus
The support electrolyte consisted of 1.4 mol L1 sodium
acetate and 2% acetic acid in methanol. Standard solutions
of elemental sulfur, 1-butanethiol and phenyl-disulde
(Acros Organics) were prepared by diluting the samples
in n-heptane solvent (Acros Organics) giving a concentration of 5.0 102 mol L1 with successive dilutions all
being done using analytical-grade chemical reagents.
A conventional electrochemical cell was used containing
a (3.0 mm diameter) glassy-carbon mercury-lm electrode
as the working electrode. A reference electrode of Ag/AgCl
(KCl 3.0 mol L1) and a platinum plate as an auxiliary
electrode was also used. The glassy-carbon electrode was
polished with alumine (0.3 lm) and washed with water
before each stage of the mercury electrodeposition.
The voltammetric measurements were carried out in an
AUTOLAB PGSTAT 30 potenciostat/galvanostat. During
the deposition step, electrode rotation was achieved by
using a rotation generator from METROHM, model
628-10.
2.2. Preparation of the MFE
Electrochemical depositing of a mercury lm on the
glassy-carbon electrode surface was achieved according to
a conventional procedure reported in the literature [32].
The electrochemical cell contained 75 lL 1.0 102
mol L1 mercury nitrate solution diluted to a nal volume
of 15 mL with an aqueous solution of 1.0 102 mol L1
lithium chloride, resulting in a 2.0 105 mol L1 solution
of mercury ions. After deaerating this solution with a ow
of nitrogen for 15 min, a potential of 0.9 V vs. Ag/AgCl
was applied to the system for 20 min while rotating at
1000 rpm. After the lm had formed, the electrode was
rinsed with deionized water and stored in an aqueous supporting electrolyte solution.
2.3. Preparation of copper column
A copper column was used with the objective of eliminating the interference of the disulde in the voltammetric
analysis [42]. A column was used and the parameters were
optimized to: (a) the diameter of the column (U = 1.5 cm),
(b) the copper mass (mCu = 10 g), (c) the height of the column (h = 20 cm), (d) the volume of the gasoline sample
(5.0 mL) and (e) the ow of the gasoline sample in the column (at atmospheric pressure). The copper used was in a
ne powder (Merck), where the size of its particles was

In all the voltammetric studies, 10.0 mL of the supporting-electrolyte, 1.4 mol L1 sodium acetate and 2% acetic
acid in methanol was transferred to the voltammetric cell
and deaerated with nitrogen. When a sample of the sulfur
compound was added to the respective concentrations of
the sulfur compounds analyzed using the square-wave-voltammetric (SWV) techniques, the voltammograms were
reported.
After optimization of the experimental conditions, the
calibration curve was obtained using disulde, mercaptan
and elemental sulfur standard solutions in the concentration interval of 2.5 107 to 6.0 106 for disulde,
2.5 107 to 7.5 106 for mercaptan and 1.0 108 to
1.0 107 for elemental sulfur using the square-wave-voltammetry technique.
2.5. Elemental sulfur, mercaptan and disulde analysis in
commercial samples of gasoline
After optimization of experimental and voltammetric
conditions for the SWV technique, commercial samples
of gasoline from the gas stations in Araraquara city were
analyzed. Each 1 mL gasoline sample was added to
10 mL of the 1.4 mol L1 sodium acetate and 2% acetic
acid in methanol [42].
However, when elemental sulfur exists along with mercaptan and disulde present in gasoline, rst the total peak
height of the solution at 0.38 and 0.70 V vs. Ag/AgCl
was measured. Then the solution was slowly passed
through a redbrown copper column (mercaptan and elemental sulfur react with copper forming cuprous mercaptide) and the peak height of the ltrate was measured
again because the disulde was not removed. The peak
height of the ltrate corresponds to the amount disulde.
The amount of mercaptan can be calculated by the peak
height of the original solution.
To study the recovery of trace sulfur compounds in samples of gasoline, a 1.0 mL sample was added to the electrolyte solution along with subsequent addition of the specic
standards.
3. Results and discussion
3.1. Formation of the mercury lm
The deposit of the mercury lm onto the glassy-carbon
electrode in lithium chloride at 1.0 102 mol L1 is carried out using the chronocoulometric technique where the

1010

D.M. Seram, N.R. Stradiotto / Fuel 87 (2008) 10071013

-600

-250

-200

-400

150

75

-150

I (A)

-300

I ()

Ip (A)

225

-500

-200

0
0

20

40

60

80

100
-1

Concentration of Sulfur (nmol L )

-100

-100
-50

0
100

0
0.0

200
0.0

-0.2

-0.4

-0.6

-0.8

-1.0

-0.2

-0.4

-1.2

-0.6

-0.8

-1.0

E (V) vs Ag/AgCl

E (V) vs Ag/AgCl

b
b

-250

500
450

-500

400

Ip ()

350

-200

300

-400

250
200

-150

I ()

I()

150

-100

-300

-1

Concentration of disulfide (mol L )

-200

-50

-100

50

0
0.0

-0.2

-0.4

100
0.0

-0.2

-0.4

-0.6

-0.8

E (V) vs Ag/AgCl

-1.0

-1.2

60

-140

50

-100
-120
-100

40
30

I ()

-80

-80

I ()

-0.8

-120

Ip (A)

-0.6

E (V) vs Ag/AgCl

-1.0

20
10

-60

-60
-40

10

12

14
-1

Concentration of mercaptan ( mol L )

-40

-20

-20

0.0

20

-0.1

-0.2

-0.3

-0.4

-0.5

-0.6

E (V) vs Ag/AgCl
40
0.0

-0.1

-0.2

-0.3

-0.4

-0.5

-0.6

E (V) vs Ag/AgCl

Fig. 1. Square-wave voltammograms of the: (a) elemental sulfur

1.0 107 mol L1; (b) disulde 2.0 106 mol L1 and (c) mercaptan
7.0 106 mol L1 in 1.4 mol L1 sodium acetate and 2% acetic acid in
methanol (f = 70 Hz and DES = 50 mV).

Fig. 2. Analytical curves constructed by means of a standard solution of

the sulfur compounds in 1.4 mol L1 sodium acetate and 2% acetic acid in
methanol using square-wave voltammetry (a) elemental sulfur; (b)
disulde and (c) mercaptan (f = 70 Hz and DES = 50 mV).

reduction of sulfur compounds happens with a strong

adsorption between sulfur and the surface of the electrode

D.M. Seram, N.R. Stradiotto / Fuel 87 (2008) 10071013

1011

Table 1
Voltammetric data obtained from the analysis of elemental sulfur, disulde and mercaptan using SWV and a MFE

Elemental sulfur
Disulde
Mercaptan

Amperometric sensitivity (lA mol1 L)

8

2.9 10
9.1 107
4.9 106

Detection limit (mol L1)

9

mercury lm. Deposition of mercury on the surface of

glassy carbon was studied at dierent time periods of 75,
150, 300, 600 and 900 s. The results showed that happens
a signicant increase of the interaction of sulfur/mercury
lm with the increase of time of deposit of the mercury
in the electrode of glass carbon, and in larger times than
600 s happened a saturation of the electrode obtaining a
current of constant peak. Also was carried out the study
of potential to be applied and rotation of the glassy carbon
electrode, being the best values in 0.9 V and 1000 rpm,
respectively.
Using the equation (L = 2.43 i.t./r2) where the product
i.t. constitutes the amount of electric charge used to make
the lm, r the radius of the electrode and L the thickness of
the mercury lm [43], a thickness of 4.5 0.5 lm was
obtained.
3.2. Methodology
The elemental sulfur presents a well-dened reduction
peak for the potential of 0.60 V vs. Ag/AgCl, as shown
in Fig. 1a. Analyzing this gure shows that this peak is
attributed to the reduction of elementary sulfur to sulde
by the transfer of two electrons in accordance the literature
[44]. In the reverse scan, an anodic peak can be observed
giving an indication of reversible characteristics
The voltammetric method is based on the electroactivity
that sulfur presents when it is reduced on the mercury-lm
electrode to sulde, generating a current that is measured
by the voltammetric analyzer. The sulfur behavior mechanism on the surface of the mercury electrode can be
explained by following mechanism:
S0 Hg0 ! HgSads

HgSads 2e ! Hg0 S2

ads

As has been suggested by Davison et al. [45] the oxidation of elemental mercury occurs owing to the great anity
of elemental sulfur to chemical adsorption at the electrode
surface. Therefore in the cathodic scan, the mercury sulphide formed has a tendency to decompose by reducing
the elemental mercury and sulphide ions.
The disulde presents a well-dened reduction peak at
about 0.65 V vs. Ag/AgCl with characteristics of being
a reversible process as shown in Fig. 1b. The disulde is
reduced to sulde in the adsorption process and by the
transfer of two electrons, as shown in Eqs. (3) and (4):

Quantication limit (mol L1)

9

3.0 0.5 10
1.6 0.7 107
4.9 0.2 107

5.5 0.3 10
5.5 0.5 107
1.6 0.6 106

RSD (%)
0.51 0.07
0.72 0.09
0.28 0.03



RSSR Hg ! RS2 Hg ads


RS2 Hg ads 2e 2H ! 2RSH Hg

3
4

The mercaptan presents a well-dened reduction peak at

a potential of 0.38 V vs. Ag/AgCl, with quasi-reversible
characteristics as shown in Fig. 1c. The analysis of this gure shows that the electrochemical reduction of mercaptan
produces disulde by the transferring two electrons as
shown by Eq. (5):
2RSH Hg 2e ! HgRS2 2H

4. Analytical performance of the procedure development

After optimizing the experimental conditions, a good
linear correlation was obtained for the analytical curve of
the sulfur compounds in 1.4 mol L1 sodium acetate and
2% acetic acid in methanol. The parameters of the concentration vs. current were calculated using the SWV technique. The analytical curve was linear with a correlation
coecient (r) of 0.9995, 0.9989 and 0.9985 for elemental
sulfur, disulde and mercaptan, respectively (Fig. 2ac).
The regression analysis data were calculated for elemental
sulfur, disulde and mercaptan as shown in the following
equation:

-100

-80

I (A)

Sulfur compounds

sample of gasoline before passing

of the copper column

S + SS

sample of gasoline after passing

of the copper column
SS

-60

SH
-40

-20

-0.2

-0.4

-0.6

-0.8

-1.0

E (V) vs Ag/AgCl

Fig. 3. Voltammograms of sulfur compounds in sample of gasoline, after

and before the sample owed through the copper column (f = 70 Hz and
DES = 50 mV).

1012

D.M. Seram, N.R. Stradiotto / Fuel 87 (2008) 10071013

I p lA 2:2 1:6  109 C mol=LFig:2a

I p lA 171:9 9:1  107 C mol=LFig:2b

Table 2
Determination of sulfur compounds in commercial fuel samples measured
using SWV and a MFE

I p lA 5:9 4:9  106 C mol=LFig:2c

Samples

Elemental sulfur
(mol L1)

Disulde
(mol L1)

Mercaptan
(mol L1)

1
2

3.5 108 0.3

2.3 108 0.6

3.7 107 0.1

2.9 107 0.8

4.2 106 0.4

3.5 106 0.5

The analytical curves obtained for the sulfur compounds

using the SWV mode enabled the determination of important electrochemical properties such as the amperometric
sensitivity (a), the detection (DL) and quantication (QL)
limits that were dened as 3 SD/b and 10 SD/b. For the
calculation of DL and QL, a theoretical procedure was followed according to the literature [44]. The values obtained
are reported in Table 1.
The precision of the developed method was veried from
the repeatability of 10 determinations of 1.0 105
mol L1 for each sulfur compound solution and the relative standard deviation (RSD%) was 0.51 0.07%,
0.72 0.09% and 0.28 0.03% for elemental sulfur, disulde and mercaptan, respectively. So, when the SWV signal
for the 1.0 105 mol L1 sulfur compound solution was
monitored for two minutes using the same mercury lm,
stability was not achieved. This is because of the absorption process that occurs on the surface of the mercury lm
and means that for each new measurement, a new mercury
lm has to be prepared.
4.1. Analysis of gasoline samples
Using the described procedure, gasoline samples were
analyzed. About 1.0 mL of gasoline was added to supporting electrolyte (sodium acetate 1.4 mol L1 and acetic acid
2% in methanol). The SWV technique was used to determine sulfur compounds in two dierent samples of conventional gasoline which were studied in triplicate. The
concentration of the sulfur compounds was calculated by
comparing their peak current with the peak current of elemental sulfur, disulde and mercaptan standard solutions,
which were measured directly. Traces of elemental sulfur,
disulde and mercaptan were found in the commercial
samples studied before and after the sample owed through
the copper column as shown in Fig. 3. Mean values and
standard deviations for these compounds are reported in
Table 2.
4.2. Recovery of sulfur compounds in gasoline
The integrity of the detection process was examined to
evaluate the recovery of sulfur compounds from commercial samples of gasoline from the gas stations in Araraquara city. The electrochemical measurements were carried
out using the SWV technique for equal quantities of gasoline (1.0 mL) in 1.4 mol L1 sodium acetate and 2% acetic
acid in methanol containing the respective concentration of
the analyzed standards with corresponding standard addition of disulde and mercaptan. However, the recovery can
not be done for elemental sulfur that is found with disulde
in the sample. Therefore the recovery was carried out

before and after the sample owed through the copper

column.
The results of the sulfur-compound measurements for
each compound analyzed, that is the data obtained for
the three repeated measurements, revealed a percentage
recovery of 105 5.4% and 98.7 3.8% of disulde and
mercaptan, respectively.
5. Conclusion
The proposed methodology, which was developed in this
work, provides a very sensitive determination of sulfur
compounds, which allows quantitative determination of
these compounds in gasoline. The results obtained by
square-wave voltammetry are adequately accurate and precise and are in good agreement with the expected detection
limits for this technique and we obtained detection limits of
the 3.0 109, 1.6 107 and 4.9 107 mol L1 for elemental sulfur, disulde and mercaptan, respectively.
Furthermore, the voltammetric technique when
employed in commercial samples presented values of
2.3 108, 2.9 107 and 3.5 106 mol L1 of elemental
sulfur, disulde and mercaptan, respectively. The main
advantage of this new method is its higher sensitivity and
its low mercury-salt toxicity in relation to the polarographic technique.
References
[1] Abass AK, Hart JP, Cowell D. Development of an amperometric
sulte biosensor based on sulte oxidase with cythchrome c, as
electron acceptor, and a screen-printed transducer. Sens Actuators B
2000;62:14853.
[2] Li M, Yuan DX, Li QL, Jin XY. Sequential analysis of dimethyl
sulfur compounds in seawater. Chin Chem Lett 2007;18:99102.
[3] Standard test method for trace anions in high purity water by ion
chromatography. ASTM D554204.
[4] Li Y, Zhao M. Simple methods for rapid determination of sulte in
food products. Food Control 2006;1:97580.
[5] Alves C, Mesquita E, Grio FM. Dessulfurizacao bacteriana de
combustveis fosseis. Biotecnologia Ambiental 1999;62:16.
[6] Modi SJ, LaCourse WR, Shansky RE. Determination of thio-based
additives for biopharmaceuticals by pulsed electrochemical detection
following HPLC. J Pharm Biomed Anal 2005;37:1925.
[7] Cezar C, Mathieu-Nolf M. Organic sulphur derivates. EMC Toxicol
Pathol 2005;2:15162.
[8] Guichard H, Bonnarme P. Development and validation of a plate
technique for screening of microorganisms that produce volatile
sulfur compounds. Anal Biochem 2005;2:299305.
[9] Bulatov AV, Rogotnev AS, Rogotnev VA, Cherepova AG. Development of state reference samples of mercaptan content in petroleum
products. Russ J Appl Chem 2004;77:20503.

D.M. Seram, N.R. Stradiotto / Fuel 87 (2008) 10071013

[10] Payzant JD, Motgomery DS, Strausz OP. Suldes in petroleum. Org
Geochem 1986;9:35769.
[11] Greenwood NN, Earnshaw A. Chemistry of the Elements. Oxford: Pergamon Press; 1985.
[12] Fairbridge RW. Encyclopedia of Geochemistry and Environmental
Sciences. New York: Van Nostrand; 1972.
[13] Shimoi T, Ibe A, Tabata S, Suzuki J, Sadamasu Y, Yasui A, Saito K.
The problem and improvement of colorimetric method for determination of sulte in foods containing sulfur compounds. J Food Hyg
Soc Japan 2004;45:3328.
[14] Standard test method for thiol (mercaptan) sulfur in gasoline,
kerosine, aviation turbine and distillate fuels (Potenciometric
Method), ASTM WK 4601 2004.
[15] Yin C, Xia D. A study of the distribution of sulfur compounds in
gasoline produced in China. Part 3. Identication of individual
suldes and thiophenes. Fuel 2004;83:43341.
[16] Padma DK. Determination of free elemental sulphur in some
petroleum products. Talanta 1989;36:5256.
[17] Ciesielski W, Zakrzewski R. Iodimetric titration of sulfur compounds
in alkaline medium. Chem Anal 2006;51:65378.
[18] Sulfur in petroleum products (X-ray spectrograc method), ASTM
WK 2216, 2003.
[19] Ramos SS, Marco DJY, Adelantado JVG, Agulles AS. Analytical
study of raw materials of zinc oxide used for enamels on industrial
ceramics: quantitative analysis of zinc, lead, and sulfur in these
samples by X-ray uorescence and ame atomic absorption spectrometry. Spectrosc Lett 2006;39:45772.
[20] Kariuki S, Morra MJ, Umiker KJ, Cheng IF. Determination of total
ionic polysuldes by dierential pulse polarography. Anal Chim Acta
2001;442:27785.
[21] Polak J, Jnacck L. Application of polarography in petrochemical
analysis. Trends Anal Chem 1989;8:14550.
[22] Lanik A, Raith J. Application of polarography methods in petroleum
laboratories. Erdoel-Erdgas 1984;100:1036.
[23] Polak J, Hozman R, Volke J. Determination of trace amounts of total
sulfur in gasolines by dierential pulse polarography. Chem Listy
1985;79:8827.
[24] Holzapfel H, Shoen K. Polarographische bestimmung des Scheuefels
in benzin. Talanta 1968;15:391402.
[25] Olofsson BR. Determination of elemental sulfur in jet fuel by
dierential pulse polarography. Anal Chim Acta 1985;177:16773.
[26] Peter F, Roset R. Dosage des thiols par polarographie a impulsions.
Anal Chim Acta 1975;79:4758.
[27] Kashiki M, Ishida K. The s.w. polarography determination of
disulde, mercaptans and free sulfur in petroleum naphta. Bull Chem
Soc Jpn 1967;40:97101.
[28] Chailapakul O, Aksharanandana P, Frelink, Einaga Y, Fujishima A.
The electrooxidation of sulfur-containing compounds at boron-doped
diamond electrode. Sens Actuators B 2001;80:193201.
[29] Pournaghi-Azar MH, Hydarpour M, Dastangoo H. Voltammetric
and amperometric determination of sulte using an aluminum
electrode modied by nickel pentacyanonitrosylferrate lm: Application to the analysis of some real samples. Anal Chim Acta
2003;497:13341.

1013

[30] Tsai DM, Kumar AS, Zen JM. A highly stable and sensitive
chemically modied screen-printed electrode for sulde analysis. Anal
Chim Acta 2006;556:14550.
[31] Monterroso SCC, Carapuca HM, Duarte AC. Performance of
poly(styrenesulfonate)-coated thin mercury lm electrodes in the
determination of lead and copper in estuarine water samples of high
salinity. Electroanalysis 2003;15:187883.
[32] Farghaly OA. Direct and simultaneous voltammetric analysis of
heavy metals in tap water samples at Assiut city: an approach to
improve the analysis time for nickel and cobalt determination at
mercury lm electrode. Microchem J 2003;75:11931.
[33] Armalis S, Kubiliene E. Mercury lm deposition and anodic stripping
using the reticulated vitreous carbon ow-through electrodes for
analysis of trace metals. Chem Anal 2001;46:71523.
[34] Ahmad N, Khan LA, Sattar A. Potentiometric stripping analysis of
heavy-metals in gasoline and dust particulate. J Chem Soc Pakistan
1991;13:748.
[35] Lo Coco F, Monotti P, Rizzotti S, Ceccon L. Determination of lead
in oil products by derivative potentiometric stripping analysis. Anal
Chim Acta 1999;386:416.
[36] Munoz E, Palmero S, Garca-Garca MA. A continuous ow system
design for simultaneous determination of heavy metals in river water
samples. Talanta 2002;57:98592.
[37] Korolczuk M. Voltammetric determination of nickel in the ow
system in the presence of an extremely large excess of cobalt and zinc.
Electroanalysis 2000;12:15024.
[38] Possari R, Carvalhal RF, Mendes RK, Kubota LT. Electrochemical
detection of cysteine in a ow system based on reductive desorption of
thiols from gold. Anal Chim Acta 2006;575:1729.
[39] Maleki N, Absalan G, Safavi A, Farjami E. Ultra trace adsorptive
stripping voltammetric determination of atrazine in soil and water
using mercury lm electrode. Anal Chim Acta 2007;581:3741.
[40] Dinckaya E, Sezginturk MK, Akylmaz E, Nil Ertas F. Sulte
determination using sulte oxidase biosensor based glassy carbon
electrode coated with thin mercury lm. Food Chem
2007;101:15404.
[41] Oliveira MF, Saczk AA, Okumura LL, Fernandes AP, Moraes M,
Stradiotto NR. Simultaneous determination of zinc, copper, lead and
cadmium in fuel ethanol by anodic stripping voltammetry using a
glassy carbon-mercury-lm electrode. Anal Bional Chem
2004;380:13540.
[42] Fernandes DR. Estudo da determinacao eletroqumica de enxofre
elementar em amostras de nafta. Tese de Mestrado. UFRJ. Instituto
de Qumica, 2004: 167.
[43] Rajeshwar K, Ibanez J. Enviromental electrochemistry fundamentals and applications in pollution abatement (1st ed.). California:
1997, 233234.
[44] Bard AJ. Encyclopedia of electrochemistry of the elements. 1st
ed. New York: Marcel Dekker; 1978. 329503.
[45] Davison W, Bue J, Devitre R. Interpretation of speciation
measurements a case-study direct polarographic-determination
of O2, Fe(II), Mn(II), S(II) and related species in anoxic waters. Pure
Appl Chem 1988;60:153548.