Spectrochimica Acta Part B 63 (2008) 800804

Contents lists available at ScienceDirect

Spectrochimica Acta Part B

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s a b

Total sulfur determination in gasoline, kerosene and diesel fuel using inductively
coupled plasma optical emission spectrometry after direct sample introduction
as detergent emulsions
Ricardo Erthal Santelli a,, Eliane Padua Oliveira a,d, Maria de Ftima Batista de Carvalho b,
Marcos Almeida Bezerra a,c, Aline Soares Freire a
a

Departamento de Geoqumica, Universidade Federal Fluminense, Outeiro So Joo Batista s/n, Centro, Niteri/RJ, 24020-150, Brazil
Centro de Pesquisas e Desenvolvimento da PETROBRS, Avaliao e Monitoramento Ambiental, Av. Horcio Macedo, 950, Cidade Universitria, Rio de Janeiro/RJ, 21941-598, Brazil
c
Universidade Estadual do Sudoeste da Bahia, Laboratrio de Qumica Analtica, Rua Jos Moreira Sobrinho s/n, Jequiezinho, Jequi/BA, 45206-190, Brazil
d
Departamento de Engenharia Qumica e de Petrleo, Universidade Federal Fluminense, Rua Passos da Ptria 156, So Domingos, Niteri/RJ, 24210-230, Brazil
b

A R T I C L E

I N F O

Article history:
Received 14 January 2008
Accepted 25 April 2008
Available online 10 May 2008
Keywords:
Sulfur determination
Petroleum derivatives
Emulsions
ICP OES
Doehlert design

A B S T R A C T
Herein, we present the development of a procedure for the determination of total sulfur in petroleumderived products (gasoline, kerosene and diesel fuel) employing inductively coupled plasma optical emission
spectrometry (ICP OES). For this procedure, samples were prepared as emulsions that were made using
concentrated nitric acid, Triton X-100, sample, and ultra pure water in proportions of 5/10/7/78% (v/v),
respectively. Sample volumes were weighed because of the density differences, and oxygen was added to the
sheat gas entrance of the ICP OES in order to decrease carbon deposition in the torch and to minimize
background effects. A Doehlert design was applied as an experimental matrix to investigate the ow ratios of
argon (sheat and plasma gas) and oxygen in relation to the signal-to-background ratio. A comparative study
among the slopes of the analytical curves built in aqueous media, surfactant/HNO3, and by spike addition for
several sample emulsions indicates that a unique solution of surfactant in acidic media can be employed to
perform the external calibration for analysis of the emulsions. The developed procedure allows for the
determination of the total sulfur content in petroleum derivatives with a limit of detection (LOD) and limit of
quantication (LOQ) of 0.72 and 2.4 g g 1, respectively. Precision values, expressed as the relative standard
deviations (% RSD, n = 10) for 12 and 400 g g 1, were 2.2% and 1.3%, respectively. The proposed procedure
was applied toward the determination of total sulfur in samples of gasoline, kerosene, and diesel fuel
commercialized in the city of Niteri/RJ, Brazil. The accuracy of the proposed method was evaluated by the
determination of the total sulfur in three different standard reference materials (SRM): NIST 2723a (sulfur in
diesel fuel oil), NIST 1616b (sulfur in kerosene), and NIST 2298 (sulfur in gasoline). The data indicate that the
methodology can be successfully applied to these types of samples. Spiking tests, conducted with the
analyzed samples, indicate that recoveries are between 97 and 103%.
2008 Elsevier B.V. All rights reserved.

1. Introduction
The total sulfur content in petroleum products is an important
variable, as sulfur compounds are associated with problems involved
in the storage, processing, transportation, and nal quality of fuel
products. Sulfur also causes severe atmospheric pollution. Sulfur
compounds, present in petroleum derivatives such as gasoline,
kerosene, diesel fuel, and fuel oil, are corrosive and can inhibit the
performance of additives in the nal products [1,2]. Further, the
combustion of fossil fuels is the principal anthropogenic source of
sulfur compounds in the atmosphere. The oxidation of sulfur
compounds upon burning emits large quantities of SOx into the
Corresponding author. Tel.: +55 21 26292192; fax: +55 21 26292234.
E-mail address: santelli@geoq.uff.br (R.E. Santelli).
0584-8547/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2008.04.020

atmosphere, causing serious pollution problems, including human

intoxication and acid rain [3]. In recent years, permissible sulfur levels
in automotive fuels have been drastically lowered by government
regulations to reduce air pollution. As such, there are demands around
the globe for the reduction of sulfur compounds in fuel products,
particularly in diesel fuel and gasoline, in order to decrease
environmental pollution in large urban areas. Today, Brazilian
governmental regulations demand that the amount of total sulfur
compounds in petroleum derivatives be decreased to the minimum
acceptable level, which may be as low as 50 g g 1 in diesel fuel and
gasoline [4].
To this end, information regarding the total sulfur concentration in
petroleum products is essential for quality control, and for assessing
the emission of this pollutant into the atmosphere. This demand
increases the need of developing fast and accurate methods with

R.E. Santelli et al. / Spectrochimica Acta Part B 63 (2008) 800804

adequate sensitivity for routine analysis of sulfur content. Several

standard methods exist for the determination of sulfur content in oil
and petroleum products, proposed by agencies such as the American
Society for Testing and Materials (ASTM). These include the D 2622-07,
D 5453-06, D 3120-06, and D 6920-07 methods [58].
Method D 2622-07 takes advantage of the characteristics of
Wavelength Dispersive X-ray Fluorescence Spectrometry (WDXFS).
Unfortunately, pooled quantication limits of this method are around
3 mg kg 1 [5]. Further, among the interfering species in this test, ethanol
is tolerated at only 8.6% (m/m), which is inadequate for the analysis of
gasoline which contains ethanol (or methanol) such as produced in
some countries as Brazil. Additionally, a careful matrix-matching
calibration is required to obtain accurate sulfur values. Method D
5453-06 measures the ultraviolet uorescence of SO2, which is
produced after sample combustion at 1075 C in an oxygen atmosphere.
The pooled detection limit is between 1 and 5 mg kg 1 [6]. Methods D
3120-06 [7] and D 6920-07 [8] are based on oxidative high temperature
pyrolisis for sample preparation and for detection, microcoulometry
titration and electrochemical, respectively. The analytical ranges of both
methods are between 1 and 100 mg kg 1 for gasoline. For diesel fuel, the
analytical range of the former lies between 1 and 40 mg kg 1, while it lies
between 3 and 1000 mg kg 1 for the latter. Both methods, which are
based on the oxidation of sulfur through the combustion of petroleum
products followed by wet chemical analysis, have certain disadvantages.
These include the requirement for large quantities of chemicals and
glassware, a time consuming protocol, and a high limit of detection [9].
Certain existing atomic spectrometric techniques are commonly used
for the determination of sulfur concentrations in petroleum derivatives.
These include inductively coupled plasma mass spectrometry (ICP-MS)
[10], inductively coupled plasma optical spectrometry (ICP OES) [11], and
X-ray uorescence spectrometry (XRFS) [12]. ICP OES is an attractive and
robust analytical technique that can be applied to the determination of
many metals and non-metals in petroleum products. ICP OES is a
consolidated and fast analytical technique, but the corresponding
procedures often require preliminary sample pretreatment. This is
needed even when robust plasma conditions are employed and it is
feasible to carry out direct sample introduction into the plasma of the
petroleum derivative through sample dilution in organic solvents. Apart
from these conditions, the direct introduction of the organic samples into
ICP OES generally causes serious problems related to overloading and
extinction of the plasma, because solvent vapors induce an undesired
instability in the plasma by changing its physical characteristics, which
affects the overall performance of the technique [1315]. Therefore, other
strategies for sample introduction into the plasma are required.
An efcient alternative for overcoming this drawback is to prepare
water-insoluble samples as emulsions. An emulsion can be formed
when a sample is evenly dispersed in an aqueous medium as microdroplets, stabilized in micelles or vesicles originating from the addition
of a suitable detergent [1618]. The use of emulsions is a simple tool for
sample preparation, and allows for the utilization of simple inorganic
aqueous standards for the calibration step, when the emulsion is
acidied with a mineral acid in the analysis of oil samples [19,20].
In this work, we present the development of an analytical
procedure for determination of total sulfur content in petroleum
derivatives using ICP OES. This method relies on sample introduction
as detergent emulsions of Triton X-100. This allows for the use of
inorganic standards for calibration, and prevents problems that may
arise from overloading and extinction of the plasma by direct
introduction of high organic content samples.

801

Table 1
Instrumental parameters used for total sulfur determination in petroleum derivatives
employing ICP OES after sample introduction as detergent emulsions
Parameter

Value

RF generator power (kW)

Nebulizer gas ow rate (L min 1)
Auxiliary gas ow rate (L min 1)
Sheat gas ow rate (L min 1)
Plasma gas ow rate (L min 1)
Oxygen ow rate (L min 1)
View height small window (mm)
View height large window (mm)
Nebulizer type
Nebulizer pressure (bar)
Integration time (s)
Stabilization time (s)
Purge gas
Analytical wavelength (nm)

1.2
0.45
0
0.2
12
0.035
15
51
Mira Mist
2.48
1
10
Ar
180.676

421) was employed in this work. For data acquisition, the Analyst JY
5.2 software was employed. An additional oxygen gas ow was used to
reduce background emissions through the oxidation of organic matter,
introduced into the plasma through the sheat gas entrance. The total
sulfur determination was carried out under the instrument conditions
presented in Table 1. An ultrasonic bath (Thornton, So Paulo, Brazil)
was employed to promote emulsions formation, and a 0.01 mg
sensibility analytical balance (Sartorius, CP 225C, Germany) was used
to weigh all petroleum derivative samples.
2.2. Reagents, solutions and samples
All reagents were prepared using ultra pure water obtained from a
purication system (Elix and Synergy, Millipore, Bedford, MA, USA), and
all chemicals used were of analytical quality. Nitric acid was of Suprapur
quality (Merck, Germany). Laboratory glassware was kept in 10% v/v nitric
acid solution overnight prior to use, then rinsed with ultra pure water and
dried in a dust free environment. Sulfur solutions were prepared by
diluting 1000 g mL 1 standard solutions (SPEX, Metuchen, USA).
Triton X-100 (Acros Organics, New Jersey, USA) was used as
surfactant to prepare all emulsions.
Certied reference materials were furnished by the NIST, and
included sulfur in gasoline (SRM 2298), sulfur in diesel fuel oil (SRM
2723a), and sulfur in kerosene (SRM 1616b). These reference materials
were used to assess procedure accuracy.
Commercial gasoline and diesel fuel samples were collected from
gas stations in Niteri/RJ, Brazil, and kerosene was acquired from a local
supermarket, and brought immediately to the laboratory for analysis.
2.3. Procedures
2.3.1. Detergent emulsion formation
The emulsion of samples and standard reference materials with
Triton X-100 (detergent emulsions) was performed according to the
following procedure: 350 L of a sample was weighed to the nearest
0.01 mg into a 5 mL volumetric ask and mixed with 250 L of
concentrated nitric acid. The resulting solution was manually shaken,
and subjected to an ultrasonic bath for 10 min. Next, 500 L of Triton X100 (10% v/v) and ultra pure water were added to obtain a total of 5 g of
the mixture, and this was again subjected to sonication for 45 min. After
formation, emulsions exhibited a milky appearance, and were stable for
at least 24 h; after which phase separation occurs. The emulsions can be
readily reconstituted by simple agitation of the mixture.

2. Experimental
2.1. Instrumentation
A Jobin Yvon (Longjumeau, France) Ultima 2 sequential ICP OES
instrument with radial view, equipped with an automatic sampler (AS

2.3.2. Investigation of gas ow ratios in the signal-to-background ratio

using a Doehlert matrix
Investigation of the ow rates of argon (plasma and sheat gas) and
oxygen, in the signal-to-background ratio was carried out using a
Doehlert matrix [21,22] for three variables according to the

802

R.E. Santelli et al. / Spectrochimica Acta Part B 63 (2008) 800804

Table 2
Doehlert experimental design and responses for optimization of gases ow rates for
total sulfur determination in fuel as emulsions

1
2
3
4
5
6
7.1
7.2
7.3
8
9
10
11
12
13

Plasma gas ow
rate (L min 1)

Sheat gas ow
rate (L min 1)

Oxygen ow
rate (L min 1)

Emission signalto-background

16 (+1)
15 (+0.5)
15 (+0.5)
15 (+0.5)
15 (+0.5)
14 (0)
14 (0)
14 (0)
14 (0)
14 (0)
13 (0.5)
13 (0.5)
13 (0.5)
13 (0.5)
12 (1)

0.5 (0)
0.35 (0.5)
0.35 (0.5)
0.65 (+0.5)
0.65 (+0.5)
0.2 (1)
0.5 (0)
0.5 (0)
0.5 (0)
0.8 (+1)
0.35 (0.5)
0.35 (0.5)
0.65 (+0.5)
0.65 (+0.5)
0.5 (0)

0.035 (0)
0 ( 0.707)
0.07 (+ 0.707)
0 ( 0.707)
0.07 (+ 0.707)
0.035 (0)
0.035 (0)
0.035 (0)
0.035 (0)
0.035 (0)
0 ( 0.707)
0.07 (+ 0.707)
0 ( 0.707)
0.07 (+ 0.707)
0.035 (0)

80.8
81.4
110.5
34.8
14.3
205.1
82.7
79.3
71.9
5.3
134.9
135.4
35.8
13.5
86.9

Figures between brackets are coded values.

the lack of t is not signicant, indicating that the model is suitable to

depict the response behavior within the experimental region.
The model tted to the data can be visualized through the response
surfaces presented in Fig. 1. The results also indicate that a decrease in
the sheat gas ow ratio is the major signicant effect in the
improvement of this response. Within the experimental region, it
was veried that the plasma gas ow rate presents no signicant
effect, and that the oxygen gas ow rate, in its central level (0.035 L
min 1), is adequate to reduce the background and avoid carbon
deposits in the inner tube of the torch. Thus, the following conditions
were selected to carry out the subsequent experiments: sheat gas ow
rate = 0.2 L min 1, plasma gas ow rate = 12 L min 1, and oxygen gas
ow rate = 0.035 L min 1.
3.2. Study of the inuence of the matrix
Matrix effects were evaluated through the slopes of the analytical
curves obtained with external and standard addition calibrations

experimental matrix presented in Table 2. As such, plasma and sheat gas

ow rates were studied at ve levels ranging from 12 to 16 L min 1 and
0.2 to 0.8 L min 1 respectively, while oxygen ow rate was assayed at
three levels ranging from 0 to 0.07 L min 1. The low level xed for the
plasma ow rate (12 L min 1) was the minimum value that could be
used according to the manufacturer's recommendations. The minimum
value employed for the sheat gas ow rate was 0.2 L min 1, which was
the minimum value capable of allowing a stable oxygen ow since this
ow was added to the sheat gas by using a Y connector piece.
As the variables involved in the study present different orders of
magnitude, the codication is very important because it enables their
investigation without the higher inuencing the lower order ones. As
such, the codication of variable levels consists of transforming each
studied value in coordinates with non-dimensional values.
3. Results and discussion
3.1. Investigation of gas ow ratios in the signal-to-background ratio
Emulsions formed from petroleum derivative samples allow for a
signicant reduction of the amount of organic material that is
introduced into the plasma when compared to solvent dilution.
Problems associated with the direct introduction of organic samples
occur due to the high vapor pressure of the analyzed fuel samples, and
thus the plasma becomes overloaded and changes its excitation
conditions. However, emulsion aerosols are still able to increase the
background due to the appearance of compounds originating from
incomplete oxidation of the organic matter, such as carbon. The
increase in background intensity results in the degradation of the
detection limits of the technique, and thereby reduces the overall
dynamic range. Molecules originating from the incomplete oxidation
also disturb the plasma and affect the precision of the measurements.
To overcome these potential issues, oxygen is employed as a simple
way to decrease the background caused by the direct introduction of
organic substances into the plasma. When high levels of organic
compounds are present, the use of oxygen (mixed with argon) in
plasma operating under robust conditions (high power and low carrier
gas ow rate) results in a stable plasma with operational conditions
that has characteristics very similar to that one operating in aqueous
solutions [14,23].
Based on data presented in Table 2, a quadratic mathematical
model was tted to describe a response behavior (emission signal-tobackground ratio) relative to changes in the levels of studied variables.
Data were evaluated using the analysis of variance (ANOVA) and the
lack of t test. The determined p-value, 0.1455 (N0.05), indicates that

Fig. 1. Response surfaces obtained in the investigation of the inuence of gases ow rates
on the signal-to-background ratio: (a) plasma gas sheat gas; (b) oxygen sheat gas.

R.E. Santelli et al. / Spectrochimica Acta Part B 63 (2008) 800804

Table 3
Comparison among analytical curves parameters obtained from solutions and
emulsions containing sulfur between 20 and 200 mg L 1 prepared in different medias

803

Table 5
Results found in the determination of total sulfur in emulsions of petroleum derivatives
samples using ICP OES and spike tests

Media

Calibration
type

Calibration
equation

R2

Sample

Added
(mg kg 1)

Found
(mg kg 1)

Recovery
(%)

Aqueousa
TX-100/HNO3 emulsionb
TX-100/HNO3 emulsiona
Gasoline emulsion
(with low sulfur content)b
Diesel emulsion
(metropolitan diesel)b
Kerosene emulsionb

External
External
External
Standard addition

y = 7977.8 [S] + 13313

y = 6578.3 [S] + 8874
y = 6582.2 [S] + 15454
y = 6485.4 [S] + 198738

0.9996
0.9995
0.9996
0.9974

Gasoline 1 (high quality)

Standard addition

y = 6558.4 [S] + 122418

0.9986

Standard addition

y = 6618.7 [S] + 9741

0.9932

0
500
0
0
0
500
1000
0
0
0
10
20

71.6 0.5
585 2
6500 56
8681 93
369 2
879 2
1400 3
349 2
409 14
18.3 0.2
28.0 0.6
37.1 0.5

103

102
103

97
94

a
b

Without oxygen.
With oxygen.

(Table 3). These curves were prepared by the addition of inorganic

standards of sulfur into the sample emulsions of gasoline with low
sulfur content, diesel fuel, and kerosene. The equations presented in
Table 3 show that the slopes for all emulsion analytical curves do not
differ signicantly, and thus the slope is sample independent. The
evaluation of the use of an aqueous analytical curve or/and an
analytical curve prepared in HNO3/Triton X-100 media was also
considered in the external calibration process. These slopes indicate
that the calibration made in aqueous media differs signicantly from
calibrations made in emulsion media. However, calibrations made in
acidic surfactant media can be applied without losses in the accuracy
of the analysis of the samples, likely due to their similar viscosities.
It is also possible to verify the increase in the system performance to
total sulfur determination by the introduction of an oxygen ow into
the plasma. This is done through intersection of the analytical curves
obtained by TX-100/HNO3 with and without oxygen in the sheat gas.
3.3. Analytical features
We assessed the analytical characteristics of the above-described
method for total sulfur determination in petroleum derivatives. The
precision of the method in sample emulsions containing 12 and
400 mg kg 1 of sulfur was in the range of 4.2 to 1.3%, respectively,
when calculated as the average relative standard deviation (RSD) of
ten consecutive measurements. The IUPAC limit of detection (LOD)
and limit of quantication (LOQ) [24] of the developed procedure
were estimated by using the RSD from ten consecutive measurements
of the blank, and also using the background equivalent concentration
(BEC) [25], according to the following equations: BEC = average blank
intensity / slope of the analytical curve; LOD = 3 BEC RSD; LOQ = 10 BEC RSD. The calculated LOD and LOQ in the samples were 0.72 and
2.4 g g 1, respectively.
3.4. Accuracy
The accuracy of the proposed procedure was evaluated from the
determination of total sulfur using external calibration in three
certied reference materials: NIST 2298 (sulfur in gasoline), NIST
2723a (sulfur in diesel fuel oil), and NIST 1616b (sulfur in kerosene)
(Table 4), and also using spiked tests performed in the analyzed
samples (Table 5). The determined values of total sulfur in the certied

Table 4
Results obtained for total sulfur determination in certied reference materials
Certied reference materials

Certied value
(mg kg 1)

Found value
(mg kg 1)

NIST 2298, sulfur in gasoline

NIST 2723a, sulfur in diesel fuel oil
NIST 1616b, sulfur in kerosene

4.7 1.3
11.0 1.1
8.41 0.12

5.1 0.5
11.1 0.5
8.0 0.3

Mean of three independent determinations and standard deviation.

Gasoline 2 (common)
Gasoline 3 (with additives)
Diesel 1 (common)

Diesel 2 (common)
Diesel 3 (with additives)
Kerosene

Mean of three independent determinations and standard deviation.

reference materials are according to the certied values, and the

results of the spiked tests indicated that recovery values were
between 94 and 103%. This conrms that the developed procedure
can be successfully employed for determination of total sulfur in these
kinds of matrices, taking advantage of emulsion sample introduction
by ICP OES.
3.5. Application
The need to control gas emissions from fossil fuel burning resulted
in a resolution (CONAMA 18/1986) approved by Conselho Nacional de
Meio Ambiente (Brazilian National Council of Environment), which
subsequently instituted the Programa de Controle da Poluio do Ar
por Veculos Automotores, PROCONVE (Car Polluted Air Control
Program). Following the initiation of PROCONVE, the Agncia Nacional
do Petrleo (ANP, National Petroleum Agency) will institute legislation
detailing the specications for automotive fuels in Brazil, following
the global demand for reduction in total sulfur content in gasoline and
diesel fuel [4]. Commercialized diesel fuels in some metropolitan
regions of Brazil, such as Rio de Janeiro, So Paulo, and Belo Horizonte,
have sulfur contents of up to 500 g g 1. In less populated Brazilian
regions, diesel fuel sulfur content is as high as 3500 g g 1 [26]. The
maximum limits for total sulfur in diesel fuel [27] and gasoline that are
being proposed by the ANP are 50 g g 1 by the year 2009 [4]. In the
United States, the Environmental Protection Agency (U.S. EPA) Tier 2
program has obliged reners to reduce gasoline sulfur content to 30 g
g 1 [28]. European Community legislation, which will be effective
from 2009, requires all fuels to contain less than 10 g g 1 of total
sulfur [29]. Thus, the development of reliable analytical procedures
that allow for the fast and accurate determination of total sulfur in
automotive fuel samples must follow the specications demanded by
future directives.
The developed procedure was employed toward the determination
of total sulfur in gasoline, diesel fuel, and kerosene samples obtained
from regions of Niteri city within the metropolitan region of Rio de
Janeiro, Brazil (Table 5). As evident, the total sulfur content in gasolines
ranged from 72 to 8680 g g 1, and all samples had sulfur in excess of
50 g g 1. For diesel, however, all samples were below 500 g g 1, and
ranged from 350 to 410 g g 1. For kerosene, there is no specic
legislation for total sulfur content, but all measured levels were as low
as only 18 g g 1.
4. Conclusions
The developed analytical procedure provides fast and efcient
determination of total sulfur content in various petroleum products by
ICP OES after sample introduction as detergent emulsions. Spike tests
and analysis of certied reference materials indicated that the
procedure has good accuracy. The limits of detection and quantication

804

R.E. Santelli et al. / Spectrochimica Acta Part B 63 (2008) 800804

of 0.72 and 2.4 g g 1, respectively, further indicate that this method can
be applied in the determination of total sulfur amounts in fuel samples
in very low concentrations, which will be demanded by CONAMA by
2009 in Brazil. The quantication limit of the proposed method is
similar to that observed in the D 2622-07 ASTM method [5]. The
developed method can be used successfully to comply with future
Brazilian and international laws and directives concerning total sulfur
content in petroleum derivatives, and provides a method that is
cheaper, faster, and free of dangerous organic solvents when compared
to conventional methods.
Acknowledgements
The authors gratefully acknowledge Conselho Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq), Coordenao de Aperfeioamento de Pessoal de Nvel Superior (CAPES) and Fundao Carlos
Chagas Filho de Amparo Pesquisa do Estado do Rio de Janeiro
(FAPERJ) for nancial support and fellowships.
References
[1] C. Yin, D. Xia, Study of the distribution of sulfur compounds in gasoline produced in
China. Part 1. A method for the determination of the distribution of sulfur
compounds in light petroleum fractions and gasoline, Fuel 80 (2001) 607610.
[2] A.O. Bender, T.M. Sarkissian, A.M. Allawi, Determination of sulphur compounds in
Iraqi natural gasoline, Fuel 68 (1989) 607609.
[3] P. O'Neil, Environmental Chemistry, 2nd ed.Chapman and Hall, London, 1993.
[4] E.R. Dauzacker, F. Palombo, Impact of the future specications for the Brazilian
gasoline formulation, Bol. Tc. Petrobrs 46 (2003) 256269.
[5] ASTM, Standard Test Method for Sulfur in Petroleum Products by Wavelength
Dispersive X-ray Fluorescence Spectrometry, Method D 2622-07, 2007.
[6] ASTM, Standard Test Method for Sulfur for Determination of Total Sulfur in Light
Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by
Ultraviolet Fluorescence, Method D 5453-06, 2006.
[7] ASTM, Standard Test Method for Trace Quantities of Sulfur in Light Liquid
Petroleum Hydrocarbons by Oxidative Microcoulometry, Method D 3120-06,
2006.
[8] ASTM, Standard Test Method for Total Sulfur in Naphthas, Distillates, Reformulated
Gasolines, Diesels, Biodiesels, and Motor Fuels by Oxidative Combustion and
Electrochemical Detection, Method D 6920-07, 2007.
[9] J. Christopher, M.B. Patel, S. Ahmed, B. Basu, Determination of sulphur in trace
levels in petroleum products by wavelength-dispersive X-ray uorescence
spectroscopy, Fuel 80 (2001) 19751979.
[10] J. Heilmann, S.F. Boulyga, K.G. Heumann, Accurate determination of sulfur in
gasoline and related fuel samples using isotope dilution ICP-MS with direct sample
injection and microwave-assisted digestion, Anal. Bioanal. Chem. 380 (2004)
190197.

[11] K.C. Weston, D.R. Hilligoss, Determination of total sulfur in gasoline by ICP OES, At.
Spectrosc. 22 (2001) 244249.
[12] N. Miskolczi, L. Bartha, J. Borszki, P. Halmos, Determination of sulfur content of
diesel fuels and diesel fuel-like fractions of waste polymer cracking, Talanta 69
(2006) 776780.
[13] C.J. Lord, Determination of trace metals in crude oil by inductively coupled plasma
mass spectrometry with microemulsion sample introduction, Anal. Chem. 63
(1991) 15941599.
[14] A.W. Broon, R.F. Browner, Effects of organic solvents in inductively coupled plasma
atomic emission spectrometry, Anal. Chem. 54 (1982) 14021410.
[15] S.J. Kumar, S. Gangadharan, Determination of trace elements in naphtha by inductively
coupled plasma mass spectrometry using water-in-oil emulsions, J. Anal. At. Spectrom.
14 (1999) 967971.
[16] M. Murillo, J. Chirinos, Use of emulsion systems for the determination of sulfur,
nickel and vanadium in heavy crude oil samples by inductively coupled plasma
atomic emission spectrometry, J. Anal. At. Spectrom. 9 (1994) 237240.
[17] A.L. Molinero, J.R. Castillo, Determination of nickel and vanadium in oil by
inductively coupled plasma atomic emission spectrometry with microemulsion
sample introduction, Anal. Lett. 31 (1998) 903911.
[18] J.L. Burguera, M. Burguera, Analytical applications of organized assemblies for online spectrometric determinations: present and future, Talanta 64 (2004)
10991108.
[19] R.M. de Souza, B.M. Mathias, I.S. Scarminio, C.L.P. da Silveira, R.Q. Auclio,
Comparison between two sample emulsication procedures for the determination
of Mo, Cr, V and Ti in diesel and fuel oil by ICP OES along with factorial design,
Microchim. Acta 153 (2006) 219225.
[20] A. Sanz-Medel, M.R.F. de la Campa, E.B. Gonzalez, M.L. Fernandez-Sanchez,
Organized surfactant assemblies in analytical atomic spectrometry, Spectrochim.
Acta Part B 54 (1999) 251287.
[21] S.L.C. Ferreira, W.N.L. dos Santos, C.M. Quintella, B.B. Neto, J.M. Bosque-Sendra,
Doehlert matrix: a chemometric tool for analytical chemistry review, Talanta 63
(2004) 10611067.
[22] R.E. Bruns, I.S. Scarminio, B.B. Neto, Statistical Design Chemometrics, Elsevier,
Amsterdam, 2006.
[23] M. Carr, K. Lebas, M. Marichy, M. Mermet, E. Poussel, J.M. Mermet, Inuence of the
sample introduction system on acid effects in inductively coupled plasma atomic
emission spectrometry, Spectrochim. Acta Part B 50 (1995) 271283.
[24] IUPAC, Analytical Chemistry Division, Nomenclature, symbols, units and their
usage in spectrochemical analysis II. data interpretation Analytical chemistry
division, Spectrochim. Acta Part B 33 (1978) 241245.
[25] F.V. Silva, L.C. Trevisan, C.S. Silva, A.R.A. Nogueira, J.A. Nbrega, Evaluation of
inductively coupled plasma optical emission spectrometers with axially and
radially viewed congurations, Spectrochim. Acta Part B 57 (2002) 19051913.
[26] Petrobrs, O ar agradece: chegou o diesel S500, Revista Petrobrs 105 (2005)
1013.
[27] CONANA. Conselho Nacional do Meio Ambiente, Ministrio do Meio Ambiente,
Resolution n 315/2002.
[28] U.S EPA, Federal Register, Control of Air Pollution from New Motor Vehicles: Tier 2
Motor Vehicle Emissions Standards and Gasoline Slfur Control Requirements
Final Rule, 2000, pp. 66986746.
[29] European Union, Commission Directive 2003/17/EC.