Fuel Processing Technology 91 (2010) 14221427

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Fuel Processing Technology

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 / f u p r o c

Development of a microwave-assisted digestion method using ICP-OES to measure metals in gum deposits of internal combustion engines
Allan N.S. Dantas, Rouse S. Costa, Sandro T. Gouveia, Gisele S. Lopes
Departamento de Qumica Analtica e Fsico-Qumica, Universidade Federal do Cear, Fortaleza, CE, Brazil

a r t i c l e

i n f o

a b s t r a c t
The heterogeneous nature of gum samples obtained from the deposits of internal combustion engines is the main difculty in accurate determination of their metal content. A microwave-assisted digestion method was implemented using factorial experimental design. The optimization of this procedure was carried out by rst evaluating the effects of variables on the response (i.e., the residual carbon content or RCC). The variables of maximum heating power, heating time and nitric acid volume were studied. The RCC response was measured by inductively coupled plasma optical emission spectrometry (ICP-OES). The time of maximum heating power was essential to obtain a desired RCC. The surface response was constructed with optimal conditions presented at 6 min and heating power of 700 W. Amounts of aluminum (Al), calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), nickel (Ni), lead (Pb) and zinc (Zn) were determined in 26 gum samples by ICP-OES. Ca, Fe, Mg and Zn were found at mg g1 levels in the samples, while Al, Cu, Mn, Ni and Pb were found at mg kg1 levels. Principal component analysis (PCA) was used to establish a correlation between the gum samples and the different metal contents. Three distinct groups were separated according to the characteristics of the collected samples. 2010 Elsevier B.V. All rights reserved.

Article history: Received 12 August 2009 Received in revised form 10 January 2010 Accepted 12 May 2010 Keywords: Metals Gum Microwave-assisted digestion ICP-OES

1. Introduction Some classes of hydrocarbons, particularly olens and diolens, are able to react slowly with the oxygen at room temperature. The oxidation of these hydrocarbons is responsible for the deposit of solids, commonly known as gums, which stick to the metal surface of internal combustion engines. Accumulation of gums can cause engine wear and may impair engine efciency, performance and durability [1]. The potential for problematic gum formation is even greater in Brazil since the gasoline used in this country, referred to as gasohol, contains between 20% and 25% v/v of ethanol [2]. Some metals are natural constituents of crude oil, while other metals can be introduced into gasoline as contaminants through contact with rening and distilling equipment or during transport and storage. Manganese compounds are also added to gasoline as anti-knocking agents since they are less toxic than lead compounds [3]. Several factors accelerate gum formation, including increases in temperature and storage time, as well as the presence of metal ions. Trace amounts of certain dissolved metals can promote fuel degradation by oxidation of organic compounds, which often leads to gum formation [2]. Metallic species are also generally undesirable

Corresponding author. Tel.: + 55 85 33669963; fax +55 85 33669982. E-mail address: gslopes@ufc.br (G.S. Lopes). 0378-3820/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2010.05.016

in automotive fuels because they are associated with engine corrosion, metal deposits on engine parts and poor fuel performance caused by oxidative decomposition [4,5]. In many countries, private and government programs have been established to develop alternative, more ecologically friendly fuels. Among these, ethanol is of increasing interest, since it is an alternative fuel and additive for gasoline. Brazil was the rst country in the world to successfully implement a large scale program to use alcohol as an automotive fuel. However, engine corrosion problems are intrinsically more severe when alcohols are used in fuels, as opposed to oil-derived fuels. These alcohol-containing fuels can dissolve inorganic salts and contain water, which play signicant roles in metal corrosion. In addition, the physical and chemical properties of alcohol alone enhance corrosion [68]. Some metals, such as nickel (Ni) and vanadium (V), are natural constituents of petroleum and are found in all petroleum-derived products, although at signicantly lower concentrations in fuels [9,10]. Iron and zinc are the main constituents of fuel containers, and they might leach into fuels during storage and transport [8]. Other metals can also be added to fuels to promote specic characteristics. For example, the following metals may be used as additives in gasoline, diesel fuel, fuel oil, kerosene and jet fuel: aluminum (Al), calcium (Ca), cerium (Ce), chromium (Cr), cobalt (Co), copper (Cu), lanthanum (La), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn), molybdenum (Mo), nickel (Ni), silicon (Si), silver (Au), sodium (Na), thallium (Tl), tin (Sn), tungsten (W), vanadium (V), zinc (Zn) and zirconium (Zr) [1113].

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Spectroanalytical methods are frequently used to determine metals in fuel matrices, although their application in metal (element) analysis requires sample digestion to avoid measurement errors. The heterogeneous nature of these samples produces unpredictable reaction behaviors. This heterogeneity presents a major obstacle in collecting accurate and precise analytical results. As such, sample analysis requires the application of sensitive methods, plus a sample decomposition method or pre-concentration procedure. Several papers have reported on pre-treatment or digestion methods for element determination in used lubricating oils and crude oils, which show chemical similarities to engine gums [9,10,1416]. Some studies have also reported simple, efcient procedures for trace element analysis whereby a detergent or co-solvent is added to fuel or oil samples to form an emulsion or microemulsion [8,12,13]. However, these procedures are not appropriate for the analysis because of the heterogeneity of gum samples obtained from deposits in internal engines. Recently, a digestion procedure was published for element analysis of gum deposits that uses a closed system with nitric acid and sulfuric acid under conventional heating [3]. This procedure was performed in 36 h, or 80% less time than dry ashing procedures. However, it was effective for only six elements (Cu, K, Fe, Ni, Si and Zn) and resulted in high standard deviations. In addition, the use of H2SO4 reagent is not appropriate for some analytical techniques. Sample preparation methods that use dry ashing, microwaveassisted digestion and combustion decomposition procedures are useful for trace element analysis as they are robust and important methodologies to assess analytical accuracy. The aim of this work was to develop a simple and fast sample preparation method to analyze trace elements in gum samples by inductively coupled plasma optical emission spectrometry (ICP-OES).

Table 2 Wavelengths of the monitored elements and the viewing position of the instrument. Element Al C Ca Cu Fe Mg Mn Ni Pb Zn Wavelength (nm) 393.153 193.030 193.030 317.933 327.393 239.562 285.213 259.372 231.604 220.353 213.857 View position Axial Axial Radial Axial Axial Axial Axial Axial Axial Axial Axial

2.2. Reagents, solutions and samples All reagents used were of analytical grade, and the water (resistivity of 18.2 M cm) was puried in a Milli-Q system (Millipore, Bedford, MA, USA). The samples were collected in departments (Fortaleza, CE, Brazil), specialized in chemical decarbonization of automotive engines. HNO3 (68% w/w) and hydrogen peroxide (H2O2) (30% v/v) (Vetec, Rio de Janeiro, Brazil) were used to prepare the samples for microwaveassisted acid digestion. Stock solutions containing carbon (5.0% w/v) were prepared using urea (CH4N2O; Vetec, Rio de Janeiro, Brazil). Standard solutions containing 0.05, 0.1, 0.2, 0.5, 1.0 and 2.5% carbon were prepared in 1.4 mol L1 HNO3. Al, Co, Cu, Fe, Mg, Ni, Pb and Zn stock aqueous solutions (1000 mg L1) were purchased from Acros Organics (New Jersey, USA). The analytical calibration curve was prepared with 1.0, 5.0, 10 and 12 mg L1 in 1.4 mol L1 HNO3. 2.3. Procedures

2. Experimental 2.1. Instrumentation All element measurements were performed using a simultaneous inductively coupled plasma optical emission spectrometer with axial and radial views (Optima 4300 Series, Perkin Elmer, USA). Table 1 provides the instrumental parameters used in the ICP-OES measurements. Table 2 lists the wavelengths and instrumental congurations (axial or radial) used for the residual carbon content (RCC) and metal determination analyses. Acid digestions were performed in a microwave oven equipped with a rotor for six quartz vessels (Multiwave, Anton Paar, Graz, Austria). The vessels were placed on a rotating turntable inside the microwave oven. The heating programs used for digestion of the samples were developed and optimized. The dry ashing digestion method used an oven (Quimis, Diadema, SP, Brazil) and digestion block (Tecnal, Piracicaba, SP, Brazil). Unscrambler Version 9.5 software (CAMO, Oslo, Norway) was used for the factorial experimental design, Surface Response Model (SRM) and principal component analysis (PCA).

Table 1 ICP-OES operating parameters for the analysis. RF power Plasma Ar gas ow Auxiliary ow Nebulizer ow Sample ow rate Replicate measurements Signal processing 1300 W 15 L min1 0.5 L min1 0.8 L min1 1.4 mL min1 3 Peak area3 pixels

A two-level full factorial design (FFD) was used to investigate the effects of the parameters (variables) on the gum digestion procedure. The variables chosen were: maximum heating power (A), heating time (B) and HNO3 volume (C). The response was measured as RCC in the digested samples. Table 3 shows the parameters and levels of the experimental design. After this rst experimental design, a new design (22 FFD) was realized where the power and time of the heating program were studied. Approximately 150 mg of gum sample was transferred to a quartz vessels after which 1.0 mL of H2O2 (30% v/v) and 2.5 mL of HNO3 (68% w/w) were added. The vessels were then closed and positioned in the microwave rotor. The heating program entailed the following four steps: 1) 300 W for 4 min; 2) 300600 W for 6 min; 3) optimization of power (parameter A) and time at this power (parameter B; varied for 16 min) and 4) maximum ventilation in the microwave cavity (power off) for 15 min to cool the vessels. After digestion, all samples were diluted with Milli-Q water in 25.0 mL volumetric asks. The blank solution was prepared using the same reagents and procedures. A gum sample was digested using the proposed optimized methodology and dry ashing digestion method.
Table 3 Variables and levels in the experimental design. Parameter A: Maximum heating power (W) B: Heating time (min) C: Nitric acid volume (mL) Higher (+) 1000 1.0 1.0 Lower () 700 6.0 4.0

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Table 4 Residual carbon content (RCC) in the experimental design study. Procedure 1 2 3 4 5a 5b
a

Power (W) 700 1000 700 1000 850 850

Time (min) 2 6 6 2 4 4

Residual carbon (%) 31.32 0.43a 4.91 0.13 9.49 0.21 32.15 0.56 21.84 0.48 22.15 0.36

200 mg of sample in a closed vessel [17]. Procedures using low volumes of acid generally require H2O2 as an auxiliary oxidizing agent. The addition of H2O2 decreases the RCC due to pressure increases that efciently oxidize organic matter at lower temperatures [18]. The digestion of gum samples requires high system pressures and temperatures to decompose the organic matter and access the metals.

3.1. Experimental design Microwave sample digestion procedures were optimized using a two-level full factorial experimental design (FFD). This experimental design allowed for the evaluation of factors affecting digestion and all possible multi-factor interactions. The following three factors were studied on two levels (maximum and minimum): power (A), time of applied power (B) and HNO3 volume (C). RCC was measured in order to estimate the responses. The two initial steps of the heating program involved rst heating sample vessels at 300 W for 4 min, followed by an increase of the power from 300 to 600 W for 6 min. For the third heating step, the maximum power (A) was changed from 600 to 1000 W for 16 min (B; the heating time variable), with an HNO3 volume (C) varying from 1 to 4 mL. Gum samples were not digested when the system was operated at minimum levels (i.e., heating program of 600 W for 1 min and containing 1 mL HNO3). Rather, we observed the presence of an emulsion (aqueous mixture with oil) in the solutions. Based on this outcome, we raised the HNO3 volume to 2.5 mL, and a new design was developed whereby the lower and higher levels of the factors were changed in the design. The amount of gum sample was set at approximately 150 mg. The complexity of organic compounds contained in these samples and the microwave-assisted digestion in closed vessels make it unsafe to work with larger sample amounts. Conversely, working with smaller samples requires more sensitive techniques for trace analysis. The analytical calibration curve for the RCC determination was established by using a urea reference solution. The wavelength monitored was 193.030 nm. The concentration range showed linear behavior in both axial and radial congurations, but no self-absorption effects were observed for the axial view under high carbon conditions at the most sensitive wavelength. Therefore, the axial viewer conguration was used to measure the RCC. Table 4 shows the experiments and RCC levels determined using the optimized gum sample digestion approach in the second experimental design.

Standard deviation for triplicate.

Table 5 Analysis of variance (ANOVA) for the 22 factorial design. r2 = 0.998 Summary A:Power(W) B:Time(min) AB Error -coefcient 1.918 * 102 5.624 0.548 Sum of squares 66.186 1.012 * 103 3.038 1.862 Mean square 66.186 1.012 * 103 3.038 0.310 F-ratio 213.257 3.262 * 103 9.790 P-value 0.000 0.000 0.0204

For the dry ashing digestion method, the sample was weighed in a glass capsule and subjected to heating (700 C) for 6 h. The procedure was repeated several times to obtain enough residue volume for element determination. After this step, the residues were placed in Teon vessels, and 1 mL of H2O2, 3 mL of hydrochloric acid (HCl): HNO3 (3:1) and 2 mL of hydrogen uoride (HF) were added. The system was heated at 120 C for 4 h in the digestion block (open system). 3. Results and discussion Frequently, methods for trace element analysis require the complete digestion of the organic fraction in samples. An acid is usually added to the mixture to combine the oxidizing agents. Reduced sample and reagent volumes are a trend in instrumental analysis. These reduced chemical volumes prevent damage to equipment parts, such as nebulizers, nebulization chambers and ICP-OES torches. The quartz torch in the axial conguration of an ICP-OES can be rapidly degraded by salt deposition from samples containing high amounts of dissolved solids. Some authors recommend using 0.42.0 mL of HNO3 to digest

Fig. 1. Surface response for the residual carbon content (RCC).

A.N.S. Dantas et al. / Fuel Processing Technology 91 (2010) 14221427 Table 6 Analytical results for the elements in the gum sample digested by the ashing procedure and proposed microwave-assisted method. Element Al (mg kg1) Ca (mg g1) Cu (mg kg1) Fe (mg g1) Mg (mg g1) Mn (mg kg1) Ni (mg kg1) Pb (mg kg1) Zn (mg g1)
a

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Dry ashing procedure 219 34a 4.95 0.5 312 48 5.58 0.65 2.28 0.20 45.2 0.9 7.32 0.35 32.4 5.9 4.42 0.35

Microwave-assisted procedure 178 12a 4.70 0.29 245 18 4.92 0.38 2.10 0.14 46.1 0.8 7.21 0.28 53.5 0.9 4.59 0.28

Standard deviation for triplicate.

The surface response of the RCC showed that the optimal conditions for digestion were at 6 min of applied power in the heating program. As previously stated, the applied power during the digestion procedure did not elicit substantial variance in the response. Therefore, the maximum applied power used in the digestions was 700 W. Fig. 1 shows the SRM for the RCC in the digested gum samples. The linear calibration range of the ICP-OES was obtained for the carbon standard solution with a correlation coefcient of r2 = 0.9961. The limit of detection (LOD) was calculated based on the background equivalent concentration (BEC) [20] according to the International Union of Pure and Applied Chemistry (IUPAC) [21]. The solution used for the blank measurements was 1.4 M HNO3, and the LOD for the axial viewer conguration was 66.5 g kg1.

The analysis of the previously mentioned effects shows that the inuence of the studied variables on the response (i.e., RCC) was signicant within a 95% condence level. The surface response model (SRM) shows the relationship between the studied variables (power and time of heating program) and the RCC. Table 5 presents the analysis of variance (ANOVA) for the proposed design using the results listed in Table 4. ANOVA was used to estimate the signicance of the main effects and interactions. The sum of the squares (SS) was used to estimate F-ratios (F). The values in the F-ratio column are the ratios of the respective mean square effect and the mean square error [19]. P-values less than 0.05 were considered statistically signicant. The -coefcient shows the estimated effect of every variable and the interaction of the variables (AB) in the plotted regression model. A negative -coefcient means that increases in the factors will result in decreased RCC values. Despite the analysis showing the signicance of the variables, time at maximum power in the heating program was essential to obtain the desired RCC content in the gum samples. A linear relationship was observed between the RCC and time at maximum power. Signicant variations in RCC values were observed with the SRM. The power of the heating program did not inuence the RCC, but the time of the applied power was essential for efcient digestion.

3.2. Microwave digestion procedure The ashing procedure was used to digest one gum sample in order to test the efciency of the optimized microwave method. In general, these approaches produce ash, which can be solubilized in diluted acid at room temperature or subjected to light heating. However, this approach was not possible for this sample. It was necessary to employ another wet procedure with HF to achieve the dissolution. The ashing procedure for the sample decomposition was performed in 36 h. Table 6 presents the elements determined in the gum samples digested by the ashing and microwave-assisted procedures. It must be mentioned that considering high temperatures in the ashing procedure, volatilization losses are expected for volatile elements and their compounds as can be observed for Pb. A t-test comparing the two decomposition procedures produced essentially the same results with a 95% condence level. The 26 gum samples were digested under optimal conditions for the proposed method, and the elemental compositions were determined by ICP-OES. Table 7 provides the analytical results and Table 8 shows the LOD and limits of quantication (LOQ) calculated for the elements according to IUPAC guidelines [21].

Table 7 Results for the 9 elements in the 26 gum samples by ICP-OES. Gum 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26
a

Al (mg kg1) 174 8a b LOD 78.4 3.3 153 6 318 12 404 15 275 9 161 5 201 4 150 6 114 3 156 7 233 9 218 10 664 15 1147 32 6013 44 518 4 509 6 385 12 1508 35 1099 22 461 10 661 8 585 9 453 12

Ca (mg g1) 4.63 0.12 2.74 0.08 2.67 0.05 2.29 0.05 4.95 0.07 3.63 0.08 6.33 0.10 3.13 0.08 3.04 0.10 6.62 0.12 7.64 0.12 3.92 0.09 6.39 0.10 2.58 0.08 1.32 0.05 0.80 0.01 30.5 2.5 6.58 0.23 0.74 0.04 1.06 0.09 0.73 0.03 1.26 0.09 0.36 0.01 0.66 0.02 0.95 0.01 0.50 0.02

Cu (mg kg1) 234 9 29.7 1.3 155 5 55.8 2.3 28.8 1.0 40.3 0.9 25.9 0.8 160 3 94.4 2.5 27.0 1.3 49.1 1.7 12.1 0.9 25.3 1.2 75.7 1.6 80.2 2.1 104 4 1882 25 151 6 2147 29 2368 32 2115 25 2673 31 226 5 702 7 2151 28 2041 29

Fe (mg g1) 4.70 0.13 0.73 0.01 1.10 0.09 0.08 0.01 0.52 0.01 0.71 0.01 0.49 0.01 0.17 0.01 0.46 0.02 0.14 0.01 0.20 0.01 0.88 0.01 0.53 0.02 4.32 0.23 0.46 0.02 0.48 0.01 5.93 1.35 9.56 1.44 0.28 0.01 0.74 0.01 2.12 0.09 0.59 0.01 0.52 0.02 0.43 0.01 0.67 0.01 0.61 0.01

Mg (mg g1) 2.02 0.09 0.17 0.01 0.33 0.01 0.10 0.01 1.29 0.05 2.10 0.06 0.48 0.01 1.29 0.03 1.26 0.05 0.34 0.01 1.52 0.12 2.79 0.22 0.38 0.01 1.79 0.21 3.79 0.20 4.29 0.32 5.25 0.38 1.40 0.20 0.54 0.02 1.07 0.09 1.08 0.06 1.22 0.04 0.61 0.02 0.30 0.01 0.59 0.01 0.75 0.02

Mn (mg kg1) 45.2 0.9 17.9 1.1 11.5 0.8 b LOD 3.34 0.19 36.8 0.9 10.7 0.5 2.25 0.15 1.81 0.08 b LOD 0.62 0.01 b LOD 6.29 0.23 47.1 1.5 5.80 0.22 5.91 0.34 91.5 2.8 71.6 1.9 6.63 0.24 10.8 0.05 26.3 0.12 74.0 2.7 15.1 0.90 45.8 2.8 9.81 0.12 12.4 0.10

Ni (mg kg1) 7.10 0.10 0.18 0.01 1.44 0.06 1.26 0.07 1.53 0.06 2.38 0.09 2.64 0.08 0.99 0.01 0.63 0.01 b LOD 0.88 0.01 3.15 0.12 3.02 0.14 6.57 0.23 9.03 0.34 9.50 0.23 113 8 22.0 0.23 5.17 0.35 47.1 1.9 33.0 0.9 18.2 1.1 26.4 1.5 24.9 1.9 47.8 3.7 8.88 0.98

Pb (mg kg1) 53.8 1.2 5.04 0.92 56.9 1.5 5.49 0.87 11.6 0.9 18.2 0.9 29.9 0.7 24.7 1.0 2.08 0.34 3.18 0.22 0.58 0.11 14.1 0.3 27.2 1.3 19.9 0.9 11.8 0.9 11.2 0.6 67.7 2.8 380 23 18.3 0.9 96.9 2.5 38.1 1.1 42.5 1.2 16.3 0.9 13.9 0.8 34.9 2.1 11.9 0.5

Zn (mg g1) 4.55 0.23 1.51 0.12 1.79 0.09 0.89 0.01 4.31 0.29 4.90 0.22 4.93 0.25 2.94 0.13 3.29 0.11 0.62 0.01 3.81 0.21 6.68 0.12 5.55 0.10 3.87 0.09 6.40 0.11 9.09 0.34 30.3 2.9 4.23 0.14 1.90 0.09 2.84 0.08 1.96 0.08 2.85 0.06 1.80 0.01 1.51 0.02 1.54 0.03 1.92 0.01

Standard deviation for triplicate.

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Table 8 Limits of detection (LOD) and limits of quantication (LOQ). Element Al Ca Cu Fe Mg Mn Ni Pb Zn Limit of detection (g kg1) 3.38 22.4 0.78 3.37 1.29 0.067 0.99 1.08 6.46 Limit of quantication (g kg1) 10.1 67.2 2.34 10.1 3.87 0.20 2.96 3.22 19.4 Correlation coefcient 0.9984 0.9973 0.9977 0.9992 0.9988 0.9997 0.9979 0.9989 0.9972

3.3. Principal component analysis (PCA) PCA is a mathematical manipulation of a data matrix with the goal of representing the variation present in many variables using a small number of factors. In other words, PCA is a bilinear modeling method that gives an interpretable overview of the main information in a

multi-dimensional data table. The information carried by the original variables is projected onto a smaller number of underlying variables called the principal components [22]. The exploratory study of data through the analysis of principal components was performed using the element amounts determined by ICP-OES (Table 7). The data were mean centered prior to analysis, which allows the analysis to consider that every variable has the same importance in the discrimination of the samples. Sample patterns were detected using the rst two principal components (PC1 and PC2 with 52 and 15% of explained variance, respectively). A plot of PC1 versus PC2 scores (Fig. 2) shows the sample distribution and relationships between scores, yielding groups that indicate similarities. The loading plot (Fig. 3) shows the distribution of variables and the relationships among the variables, as well as the relative contribution of each to the data variability. Sample 17 presented a large residue value over 10%, and was therefore considered an outlier. The Mn variable was also separated from the data set, as it was not detected in all of the samples by ICPOES.

Fig. 2. PCA scores plot.

Fig. 3. PCA loadings plot.

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The joint analysis of the scores and the loading plots allows for the evaluation of the relationships between samples and variables, making it possible to establish correlations and observe differences among the three groups. The rst and largest group was formed by samples 19, 20, 21, 22, 23, 24, 25 and 26 because these samples had higher Cu levels. This group of gum samples was collected from motor vehicle engines that had rotated between 20,000 and 40,000 km. However, these samples are from the same automobile maker and/or manufacturer; therefore, the Cu amounts found in these samples could come from the material of the motor engine parts and be in the sample due to corrosion. Only sample 20 was from a different car maker and/or manufacturer, and it rotated 97,000 km. The higher copper amount was probably caused by the fuel quality used in automobiles. The second group included samples 6, 12, 14, 15 and 16 and presented high amounts of Zn. In this case, the gum samples were collected from engines that operated for 30,000 to 60,000 km. The gum samples were not representative of samples taken from the same car manufacturer, and the Zn content was probably corrosion of motor engine parts. The third group presented high levels of Ca and was formed in samples 5, 7, 11 and 13. These samples were from engines operated for more than 100,000 km. According to Mello and Monteiro, Ca and Mg are present as formulation components in some motor oils [23]. 4. Conclusions This study provides a simple and efcient method for the digestion of gum samples with the aim of element analysis by ICP-OES. The best experimental parameters were established by using a multivariate approach based on factorial designs. These experimental designs showed that while the applied level of heat did not inuence the response (RCC), the heating time was essential for efcient digestion. The ashing procedure was used to digest one gum sample in order to check the accuracy of the microwave-assisted method. The two methods provided essentially the same results within a 95% condence level. An exploratory study of data relationships through PCA was performed using element amounts determined by ICP-OES. Joint analysis of scores and loading plots allowed for the evaluation of relationships between samples and variables. This analysis made it possible to suggest correlations between the corrosion of engine components and fuel quality used in these automobiles. Acknowledgements The authors are grateful to the CNPq and CTPETRO for the nancial support and for the A.N.S. Dantas fellowship. References
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