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Spectrochimica Acta Part B 63 (2008) 800–804

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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 Fátima Batista de Carvalho b,
Marcos Almeida Bezerra a,c, Aline Soares Freire a

Departamento de Geoquímica, Universidade Federal Fluminense, Outeiro São João Batista s/n, Centro, Niterói/RJ, 24020-150, Brazil
Centro de Pesquisas e Desenvolvimento da PETROBRÁS, Avaliação e Monitoramento Ambiental, Av. Horácio Macedo, 950, Cidade Universitária, Rio de Janeiro/RJ, 21941-598, Brazil
Universidade Estadual do Sudoeste da Bahia, Laboratório de Química Analítica, Rua José Moreira Sobrinho s/n, Jequiezinho, Jequié/BA, 45206-190, Brazil
Departamento de Engenharia Química e de Petróleo, Universidade Federal Fluminense, Rua Passos da Pátria 156, São Domingos, Niterói/RJ, 24210-230, Brazil



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

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 flow 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
quantification (LOQ) of 0.72 and 2.4 μg g− 1, respectively. Precision values, expressed as the relative standard
deviations (% RSD, n = 10) for 12 and 400 μg 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 Niterói/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 final 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 final 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: (R.E. Santelli).
0584-8547/$ – see front matter © 2008 Elsevier B.V. All rights reserved.

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 μg 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

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 μL of a sample was weighed to the nearest 0. and subjected to an ultrasonic bath for 10 min. in the signal-to-background ratio was carried out using a Doehlert matrix [21. Millipore. This method relies on sample introduction as detergent emulsions of Triton X-100. Santelli et al. among the interfering species in this test.2. the Analyst JY 5. and all chemicals used were of analytical quality. Bedford. Certified reference materials were furnished by the NIST. CP 225C. After formation. An ultrasonic bath (Thornton. which is produced after sample combustion at 1075 °C in an oxygen atmosphere. Reagents. In this work. Investigation of gas flow ratios in the signal-to-background ratio using a Doehlert matrix Investigation of the flow rates of argon (plasma and sheat gas) and oxygen. USA) was used as surfactant to prepare all emulsions. when the emulsion is acidified with a mineral acid in the analysis of oil samples [19. proposed by agencies such as the American Society for Testing and Materials (ASTM).22] for three variables according to the . Germany).48 1 10 Ar 180. microcoulometry titration and electrochemical. São Paulo. Certain existing atomic spectrometric techniques are commonly used for the determination of sulfur concentrations in petroleum derivatives. ICP OES is a consolidated and fast analytical technique. ethanol is tolerated at only 8. and D 6920-07 methods [5–8]. the analytical range of the former lies between 1 and 40 mg kg− 1.2. Procedures 2.01 mg into a 5 mL volumetric flask and mixed with 250 μL of concentrated nitric acid. Method D 2622-07 takes advantage of the characteristics of Wavelength Dispersive X-ray Fluorescence Spectrometry (WDXFS). This allows for the use of inorganic standards for calibration. and included sulfur in gasoline (SRM 2298).2 12 0. inductively coupled plasma optical spectrometry (ICP OES) [11].035 15 51 Mira Mist 2. Laboratory glassware was kept in 10% v/v nitric acid solution overnight prior to use. Next. The total sulfur determination was carried out under the instrument conditions presented in Table 1. Additionally. which affects the overall performance of the technique [13–15]. MA.3. 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 flow rate (L min− 1) Auxiliary gas flow rate (L min− 1) Sheat gas flow rate (L min− 1) Plasma gas flow rate (L min− 1) Oxygen flow 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. 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. and allows for the utilization of simple inorganic aqueous standards for the calibration step. equipped with an automatic sampler (AS 2. which are based on the oxidation of sulfur through the combustion of petroleum products followed by wet chemical analysis. while it lies between 3 and 1000 mg kg− 1 for the latter. stabilized in micelles or vesicles originating from the addition of a suitable detergent [16–18].1.1. Instrumentation A Jobin Yvon (Longjumeau. but the corresponding procedures often require preliminary sample pretreatment. USA). 2. other strategies for sample introduction into the plasma are required. and brought immediately to the laboratory for analysis. because solvent vapors induce an undesired instability in the plasma by changing its physical characteristics. and a 0. Apart from these conditions. then rinsed with ultra pure water and dried in a dust free environment.3. Metuchen. and prevents problems that may arise from overloading and extinction of the plasma by direct introduction of high organic content samples. These include inductively coupled plasma mass spectrometry (ICP-MS) [10]. Nitric acid was of Suprapur® quality (Merck. and this was again subjected to sonication for 45 min. Both methods. Sulfur solutions were prepared by diluting 1000 μg mL− 1 standard solutions (SPEX.3. emulsions exhibited a milky appearance. These include the D 2622-07. 2. have certain disadvantages. 500 μL of Triton X100 (10% v/v) and ultra pure water were added to obtain a total of 5 g of the mixture. a careful matrix-matching calibration is required to obtain accurate sulfur values. The emulsions can be readily reconstituted by simple agitation of the mixture.2 0. and sulfur in kerosene (SRM 1616b). Therefore. An emulsion can be formed when a sample is evenly dispersed in an aqueous medium as microdroplets. Brazil) was employed to promote emulsions formation. The resulting solution was manually shaken. Triton X-100 (Acros Organics. An additional oxygen gas flow was used to reduce background emissions through the oxidation of organic matter. which is inadequate for the analysis of gasoline which contains ethanol (or methanol) such as produced in some countries as Brazil. solutions and samples All reagents were prepared using ultra pure water obtained from a purification system (Elix and Synergy. Brazil. and were stable for at least 24 h. and X-ray fluorescence 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.6% (m/m). These reference materials were used to assess procedure accuracy.01 mg sensibility analytical balance (Sartorius. The pooled detection limit is between 1 and 5 mg kg− 1 [6]. An efficient alternative for overcoming this drawback is to prepare water-insoluble samples as emulsions. Unfortunately. Experimental 2.45 0 0. USA).676 421) was employed in this work. introduced into the plasma through the sheat gas entrance. the direct introduction of the organic samples into ICP OES generally causes serious problems related to overloading and extinction of the plasma. For data acquisition. For diesel fuel. Method D 5453-06 measures the ultraviolet fluorescence of SO2.20]. D 3120-06. / Spectrochimica Acta Part B 63 (2008) 800–804 adequate sensitivity for routine analysis of sulfur content. 2. Several standard methods exist for the determination of sulfur content in oil and petroleum products. France) Ultima 2 sequential ICP OES instrument with radial view. The use of emulsions is a simple tool for sample preparation. we present the development of an analytical procedure for determination of total sulfur content in petroleum derivatives using ICP OES. respectively. Further. after which phase separation occurs. The analytical ranges of both methods are between 1 and 100 mg kg− 1 for gasoline. New Jersey. Commercial gasoline and diesel fuel samples were collected from gas stations in Niterói/RJ. These include the requirement for large quantities of chemicals and glassware. Methods D 3120-06 [7] and D 6920-07 [8] are based on oxidative high temperature pyrolisis for sample preparation and for detection. pooled quantification limits of this method are around 3 mg kg− 1 [5].E. and kerosene was acquired from a local supermarket. D 5453-06. and a high limit of detection [9].R. a time consuming protocol.2 software was employed. sulfur in diesel fuel oil (SRM 2723a). Germany) was used to weigh all petroleum derivative samples.

035 L min− 1).035 (0) 0 (− 0. As such. Problems associated with the direct introduction of organic samples occur due to the high vapor pressure of the analyzed fuel samples.1455 (N0. The model fitted to the data can be visualized through the response surfaces presented in Fig.035 (0) 0. in its central level (0.802 R. 1.5) 14 (0) 14 (0) 14 (0) 14 (0) 14 (0) 13 (−0.5) 0.65 (+0. Response surfaces obtained in the investigation of the influence of gases flow rates on the signal-to-background ratio: (a) plasma gas × sheat gas.5 (0) 0.2. Within the experimental region. Investigation of gas flow ratios in the signal-to-background ratio Emulsions formed from petroleum derivative samples allow for a significant reduction of the amount of organic material that is introduced into the plasma when compared to solvent dilution.035 (0) 0 (− 0.707) 0. As the variables involved in the study present different orders of magnitude.05).07 (+ 0. When high levels of organic compounds are present.5) 0. As such. oxygen is employed as a simple way to decrease the background caused by the direct introduction of organic substances into the plasma.8 13.7 79.8 (+1) 0.3 205.3 134.707) 0. 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.2 (−1) 0.5) 12 (−1) 0.5) 0.707) 0.4 110.5) 15 (+0.5 (0) 0.5) 13 (−0.E. Based on data presented in Table 2.707) 0 (− 0.5) 0. (b) oxygen× sheat gas.5 (0) 0. To overcome these potential issues.23].35 (−0. and oxygen gas flow rate = 0.035 (0) 0.07 (+ 0.65 (+0.3 71.5) 15 (+0.8 14.707) 0.035 (0) 0.8 81.2 L min− 1.035 (0) 80.07 (+ 0.2 to 0.5) 15 (+0. indicating that the model is suitable to depict the response behavior within the experimental region. However.07 L min− 1. it was verified that the plasma gas flow rate presents no significant effect.5) 13 (−0.5) 13 (−0.9 Figures between brackets are coded values. while oxygen flow rate was assayed at three levels ranging from 0 to 0.35 (−0. Study of the influence 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. the use of oxygen (mixed with argon) in plasma operating under robust conditions (high power and low carrier gas flow rate) results in a stable plasma with operational conditions that has characteristics very similar to that one operating in aqueous solutions [14. Molecules originating from the incomplete oxidation also disturb the plasma and affect the precision of the measurements.3 8 9 10 11 12 13 Plasma gas flow rate (L min− 1) Sheat gas flow rate (L min− 1) Oxygen flow rate (L min− 1) Emission signalto-background 16 (+1) 15 (+0. and that the oxygen gas flow rate.5 (0) 0. The low level fixed for the plasma flow rate (12 L min− 1) was the minimum value that could be used according to the manufacturer's recommendations.5) 0.9 135. The minimum value employed for the sheat gas flow rate was 0. is adequate to reduce the background and avoid carbon deposits in the inner tube of the torch.5 34.707) 0.5 86. indicates that Fig.707) 0 (− 0. the codification is very important because it enables their investigation without the higher influencing the lower order ones. . 1.707) 0.1 82.9 5.65 (+0. 3. the following conditions were selected to carry out the subsequent experiments: sheat gas flow rate = 0.035 L min− 1.07 (+ 0.5) 0. the codification of variable levels consists of transforming each studied value in coordinates with non-dimensional values.2 L min− 1.5) 0. The increase in background intensity results in the degradation of the detection limits of the technique.35 (−0.1 7. Results and discussion 3. plasma gas flow rate = 12 L min− 1. and thus the plasma becomes overloaded and changes its excitation conditions. Thus.65 (+0.5 (0) 0. the lack of fit is not significant. a quadratic mathematical model was fitted to describe a response behavior (emission signal-tobackground ratio) relative to changes in the levels of studied variables.4 35. plasma and sheat gas flow rates were studied at five levels ranging from 12 to 16 L min− 1 and 0.035 (0) 0.5) 0. 0. The determined p-value. Data were evaluated using the analysis of variance (ANOVA) and the lack of fit test.1. / Spectrochimica Acta Part B 63 (2008) 800–804 Table 2 Doehlert experimental design and responses for optimization of gases flow rates for total sulfur determination in fuel as emulsions 1 2 3 4 5 6 7. The results also indicate that a decrease in the sheat gas flow ratio is the major significant effect in the improvement of this response. and thereby reduces the overall dynamic range. which was the minimum value capable of allowing a stable oxygen flow since this flow was added to the sheat gas by using a Y connector piece.35 (−0. 3. Santelli et al.8 L min− 1 respectively.2 7.

PROCONVE (Car Polluted Air Control Program).2 [S] + 15454 y = 6485. according to the following equations: BEC = average blank intensity / slope of the analytical curve.5. The calculated LOD and LOQ in the samples were 0.2 28.12 5. diesel fuel sulfur content is as high as 3500 μg g− 1 [26].0 ± 0. and thus the slope is sample independent. likely due to their similar viscosities. but all measured levels were as low as only 18 μg g− 1.3 ± 0. which subsequently instituted the Programa de Controle da Poluição do Ar por Veículos Automotores.4 [S] + 122418 0.2 to 1. 3. Santelli et al. NIST 2723a (sulfur in diesel fuel oil). sulfur in gasoline NIST 2723a.6 ± 0. 3. The developed procedure was employed toward the determination of total sulfur in gasoline. the Environmental Protection Agency (U.5 11. when calculated as the average relative standard deviation (RSD) of ten consecutive measurements. the Agência Nacional do Petróleo (ANP.7 [S] + 9741 0.4. This confirms that the developed procedure can be successfully employed for determination of total sulfur in these kinds of matrices.72 and 2. 4. reference materials are according to the certified values. requires all fuels to contain less than 10 μg g− 1 of total sulfur [29].1 8. In less populated Brazilian regions. European Community legislation. National Petroleum Agency) will institute legislation detailing the specifications for automotive fuels in Brazil. The IUPAC limit of detection (LOD) and limit of quantification (LOQ) [24] of the developed procedure were estimated by using the RSD from ten consecutive measurements of the blank.9995 0. It is also possible to verify the increase in the system performance to total sulfur determination by the introduction of an oxygen flow into the plasma. such as Rio de Janeiro. respectively. and NIST 1616b (sulfur in kerosene) (Table 4). São Paulo. 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. 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. / Spectrochimica Acta Part B 63 (2008) 800–804 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. These curves were prepared by the addition of inorganic standards of sulfur into the sample emulsions of gasoline with low sulfur content.3%.3 [S] + 8874 y = 6582. the total sulfur content in gasolines ranged from 72 to 8680 μg g− 1. following the global demand for reduction in total sulfur content in gasoline and diesel fuel [4]. Thus. and all samples had sulfur in excess of 50 μg g− 1.0 ± 1. The equations presented in Table 3 show that the slopes for all emulsion analytical curves do not differ significantly. sulfur in kerosene 4. LOQ = 10 × BEC × RSD. (Table 3). and the results of the spiked tests indicated that recovery values were between 94 and 103%. However. The limits of detection and quantification .5 8. however. respectively. For kerosene. EPA) Tier 2 program has obliged refiners to reduce gasoline sulfur content to 30 μg g− 1 [28]. For diesel.4 μg g− 1. the development of reliable analytical procedures that allow for the fast and accurate determination of total sulfur in automotive fuel samples must follow the specifications demanded by future directives. Following the initiation of PROCONVE. With oxygen. diesel fuel.8 [S] + 13313 y = 6578. and kerosene samples obtained from regions of Niterói city within the metropolitan region of Rio de Janeiro.S. This is done through intersection of the analytical curves obtained by TX-100/HNO3 with and without oxygen in the sheat gas. all samples were below 500 μg g− 1. and also using the background equivalent concentration (BEC) [25].9974 Gasoline 1 (high quality) Standard addition y = 6558.41 ± 0.3 11. Accuracy The accuracy of the proposed procedure was evaluated from the determination of total sulfur using external calibration in three certified reference materials: NIST 2298 (sulfur in gasoline).7 ± 1.9986 Standard addition y = 6618.1 ± 0. As evident. calibrations made in acidic surfactant media can be applied without losses in the accuracy of the analysis of the samples.5 585 ± 2 6500 ± 56 8681 ± 93 369 ± 2 879 ± 2 1400 ± 3 349 ± 2 409 ± 14 18. there is no specific legislation for total sulfur content. The precision of the method in sample emulsions containing 12 and 400 mg kg− 1 of sulfur was in the range of 4.3. and also using spiked tests performed in the analyzed samples (Table 5).9996 0.3 Mean of three independent determinations and standard deviation. and ranged from 350 to 410 μg g− 1. and Belo Horizonte. These slopes indicate that the calibration made in aqueous media differs significantly from calibrations made in emulsion media. Brazil (Table 5). which will be effective from 2009.1 ± 0. 3.9932 0 500 0 0 0 500 1000 0 0 0 10 20 71. The maximum limits for total sulfur in diesel fuel [27] and gasoline that are being proposed by the ANP are 50 μg g− 1 by the year 2009 [4]. Commercialized diesel fuels in some metropolitan regions of Brazil.9996 0. 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). The determined values of total sulfur in the certified Table 4 Results obtained for total sulfur determination in certified reference materials Certified reference materials Certified value (mg kg− 1) Found value (mg kg− 1) NIST 2298. Spike tests and analysis of certified reference materials indicated that the procedure has good accuracy. and kerosene. have sulfur contents of up to 500 μg g− 1. sulfur in diesel fuel oil NIST 1616b. Analytical features We assessed the analytical characteristics of the above-described method for total sulfur determination in petroleum derivatives. LOD = 3 × BEC × RSD.4 [S] + 198738 0. taking advantage of emulsion sample introduction by ICP OES. diesel fuel. In the United States.E.6 37.5 – 103 – – – 102 103 – – – 97 94 a b Without oxygen.1 ± 0. Conclusions The developed analytical procedure provides fast and efficient determination of total sulfur content in various petroleum products by ICP OES after sample introduction as detergent emulsions.R.0 ± 0.

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