Spectrochimica Acta Part B 63 (2008) 800804

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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 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

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.

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

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

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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. 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

Table 1 Instrumental parameters used for total sulfur determination in petroleum derivatives employing ICP OES after sample introduction as detergent emulsions Parameter 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) Value 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. 2.3.2. 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

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Table 2 Doehlert experimental design and responses for optimization of gases ow rates for total sulfur determination in fuel as emulsions Plasma gas ow rate (L min 1) 1 2 3 4 5 6 7.1 7.2 7.3 8 9 10 11 12 13 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) Sheat gas ow rate (L min 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) Oxygen ow rate (L min 1) 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) Emission signalto-background 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

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

Figures between brackets are coded values.

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

803

Table 5 Results found in the determination of total sulfur in emulsions of petroleum derivatives samples using ICP OES and spike tests Sample Gasoline 1 (high quality) Gasoline 2 (common) Gasoline 3 (with additives) Diesel 1 (common) Added (mg kg 1) 0 500 0 0 0 500 1000 0 0 0 10 20 Found (mg kg 1) 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 Recovery (%) 103 102 103 97 94

Calibration type External External External Standard addition Standard addition Standard addition

Calibration equation y = 7977.8 [S] + 13313 y = 6578.3 [S] + 8874 y = 6582.2 [S] + 15454 y = 6485.4 [S] + 198738 y = 6558.4 [S] + 122418 y = 6618.7 [S] + 9741

R2 0.9996 0.9995 0.9996 0.9974 0.9986 0.9932

Without oxygen. With oxygen.

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

(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

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

Table 4 Results obtained for total sulfur determination in certied reference materials Certied reference materials NIST 2298, sulfur in gasoline NIST 2723a, sulfur in diesel fuel oil NIST 1616b, sulfur in kerosene Certied value (mg kg 1) 4.7 1.3 11.0 1.1 8.41 0.12 Found value (mg kg 1) 5.1 0.5 11.1 0.5 8.0 0.3

Mean of three independent determinations and standard deviation.

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

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.