Characterization of Metal and Trace Element Contents of Particulate Matter (PM 10 ) Emitted by Vehicles Running on Brazilian Fuels—Hydrated Ethanol and Gasoline with 22% of Anhydrous

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Characterization of Metal and Trace Element Contentsof Particulate Matter (PM10) Emitted by VehiclesRunning on Brazilian Fuels—Hydrated Ethanol andGasoline with 22% of Anhydrous EthanolMoacir Ferreira da Silva a , João Vicente de Assunção b , Maria de Fátima Andrade c & CéliaR. Pesquero ba Environmental Company of the State of São Paulo, CETESB , São Paulob School of Public Health of the University of São Paulo , São Pauloc Institute of Astronomy, Geophysics and Atmospheric Sciences of the University of SãoPaulo , São Paulo, BrazilPublished online: 17 Jun 2010.

To cite this article: Moacir Ferreira da Silva , João Vicente de Assunção , Maria de Fátima Andrade & Célia R. Pesquero (2010)Characterization of Metal and Trace Element Contents of Particulate Matter (PM10) Emitted by Vehicles Running on BrazilianFuels—Hydrated Ethanol and Gasoline with 22% of Anhydrous Ethanol, Journal of Toxicology and Environmental Health, Part A:Current Issues, 73:13-14, 901-909, DOI: 10.1080/15287391003744849

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Journal of Toxicology and Environmental Health, Part A, 73:901–909, 2010Copyright © Taylor & Francis Group, LLCISSN: 1528-7394 print / 1087-2620 onlineDOI: 10.1080/15287391003744849

CHARACTERIZATION OF METAL AND TRACE ELEMENT CONTENTS OF PARTICULATE MATTER (PM10) EMITTED BY VEHICLES RUNNING ON BRAZILIAN FUELS—HYDRATED ETHANOL AND GASOLINE WITH 22% OF ANHYDROUS ETHANOL

Moacir Ferreira da Silva1, João Vicente de Assunção2, Maria de Fátima Andrade3, Célia R. Pesquero2

1Environmental Company of the State of São Paulo, CETESB, São Paulo2School of Public Health of the University of São Paulo, São Paulo3Institute of Astronomy, Geophysics and Atmospheric Sciences of the University of São Paulo, São Paulo, Brazil

Emission of fine particles by mobile sources has been a matter of great concern due to itspotential risk both to human health and the environment. Although there is no evidence thatone sole component may be responsible for the adverse health outcomes, it is postulatedthat the metal particle content is one of the most important factors, mainly in relation to oxi-dative stress. Data concerning the amount and type of metal particles emitted by automotivevehicles using Brazilian fuels are limited. The aim of this study was to identify inhalable par-ticles (PM10) and their trace metal content in two light-duty vehicles where one was fueledwith ethanol while the other was fueled with gasoline mixed with 22% of anhydrous ethanol(gasohol); these engines were tested on a chassis dynamometer. The elementary composi-tion of the samples was evaluated by the particle-induced x-ray emission technique. Theexperiment showed that total emission factors ranged from 2.5 to 11.8 mg/km in the gasoholvehicle, and from 1.2 to 3 mg/km in the ethanol vehicle. The majority of particles emittedwere in the fine fraction (PM2.5), in which Al, Si, Ca, and Fe corresponded to 80% of the totalweight. PM10 emissions from the ethanol vehicle were about threefold lower than those ofgasohol. The elevated amount of fine particulate matter is an aggravating factor, consideringthat these particles, and consequently associated metals, readily penetrate deeply into therespiratory tract, producing damage to lungs and other tissues.

The heavy concentration of automotive vehi-cles in urban centers constitutes the main sourceof environmental contaminants, due to emissionsinto the atmosphere (Kleeman et al., 2000).Located in southeastern Brazil, the São PauloMetropolitan Area has 19 million people distrib-uted in an urban area of 1747 km2, with morethan 7.8 million vehicles. From this total, thehydrated ethanol-powered vehicles represent12.3%, while the Brazilian gasoline-powered (a

blend of 22% anhydrous ethanol and 78% gaso-line, designated as gasohol) vehicles represent65%. This situation is responsible for the emis-sion of about 1.44 million tons per year of car-bon monoxide (CO), 347.36 thousand tons peryear of hydrocarbons (HC), 317.76 thousandtons per year of nitrogen oxides (NOx), and 3.19thousand tons per year of sulfur oxides (SOx)(CETESB, 2007). In addition to the gaseousemissions, these automotive vehicles are also

The authors express their gratitude to the Environmental Company of the State of São Paulo (CETESB); the Department of Atmo-spheric Sciences of the Institute of Astronomy, Geophysics and Atmospheric Sciences (IAG/USP); the Laboratory of Analysis of Materialsby Ionic Beam (LAMFI) of the Institute of Physics (IF/USP); and the Department of Environmental Health of the School of Public Healthof the University of São Paulo (FSP/USP).

Address correspondence to Moacir Ferreira da Silva, Avenida Professor Frederico Hermann Junior 345, 05459.900–São Paulo SP,Brazil. E-mail: [email protected]

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902 M. FERREIRA DA SILVA ET AL.

responsible for 11.6 thousand tons per year ofparticulate matter, PM10 (CETESB, 2007), whichcontains metal particles originating from (1)wearing down of the inner parts of engines, (2)abrasion of catalytic converters, and (3) use offuels, lubricant oils, and fuel additives.

Studies indicated that fine particles pro-duce greater toxicity than coarse particles tohumans, and are even more harmful thansome gaseous pollutants (Vedal, 1997; Krewski& Rainham, 2007). Some epidemiologicalstudies revealed a strong association betweenelevated fine particle concentration and anincrease in morbidity and mortality, includingexacerbations of respiratory-tract diseases anddeaths associated with cardiorespiratory prob-lems (Petrucci et al., 2000; Pope et al., 2002;Dominici et al., 2005; Krewski et al., 2005;Yang et al., 2004). Furthermore, metal com-pounds present in these particles act as anaggravating factor due to their contribution tooxidative stress (Dreher et al., 1997; Valavanidiset al., 2000), as well as to their sensitizing,allergic, and carcinogenic effects (Pope et al.,2002; Krweski & Rainham, 2007). Informationregarding metal concentration in internal com-bustion engine exhaust emissions is quite lim-ited and few nationwide data are available. Astudy conducted by Carvalho-Oliveira et al.(2005) in the city of São Paulo, Brazil, corre-lated the atmospheric fine particle compositionwith the mutagenic activity of diesel bus emis-sions. The study was performed during a busstrike (April 6–8, 2003) and results were com-pared with data gathered on a day without thestrike (April 15 of the same year). This compar-ison showed that trace metal concentration inthe atmosphere was lower during the strike,when diesel buses did not circulate.

Concerning vehicle emissions, some plati-num-group elements (PGE), also known asplatinum-group metals (PGM), are especiallyrelevant due to their frequent use in automo-tive catalytic converters. Morcelli et al. (2005)analyzed samples of soil collected near a roadwith heavy traffic (Highway SP 348) to deter-mine the distribution of Pt, Pd, and Rh. Thesamples were collected at four different loca-tions selected according to traffic volume and

various driving conditions: stopping, starting,and constant speed. The amounts of Pt, Pd,and Rh found at each of the points rangedfrom 0.3 to 17 ng/g, from 1.1 to 58 ng/g, andfrom 0.07 to 8.2 ng/g, respectively. To date,there is no legal limit for atmospheric concen-tration of metals in Brazil, except for inorganicPb in the state of Sao Paulo, established at1.5 μg/m3 (CETESB, 2007).

This aim of this study was to determine theconcentrations of inhalable particulate matterof aerodynamic diameter (da) ≤10 μm (PM10),which was divided into two portions: (1) finefraction (PM2.5) and (2) coarse fraction (PM2.5–10).The study was also undertaken to identifymetal elements associated with particles emit-ted by vehicles using hydrated ethanol andgasohol, in consideration of the fact that theseare used in Brazilian vehicles as fuel sources.

MATERIALS AND METHODS

Test Vehicles and Fuels

Two light-duty vehicles were assessed on achassis dynamometer (Clayton ECE-50) at theVehicle Emission Laboratory of the Environ-mental Company of São Paulo (CETESB). Thevehicles were tested using the standardizeddriving cycle (ABNT, 2005), which is identicalto the one used in the U.S. Federal Test Proce-dure 75 (USFTP-75). This driving cycle is com-posed of three parts including cold, stabilized,and hot phases that simulate urban drivingconditions and includes a series of accelera-tions, decelerations, and idling. The results areshown in Table 1.

The vehicles were equipped with elec-tronic fuel injection systems and catalytic con-verters (a component of emission controlsystems used to reduce the discharge of nox-ious and polluting gases from the internal-com-bustion engine). According to Brazilianlegislation, such equipment must operate inperfect conditions up to at least 80,000 km(Conama, 2002).

Assays with vehicle 1 were planned usingthe following fuels: commercial gasohol,premium gasohol (high-octane, low-sulfur

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content), gasohol for standard emission, withand without fuel additive, and intentionallyadulterated gasohol with and without fueladditive. The fuels used in vehicle 2 included:commercial hydrated ethanol, hydratedethanol for standard emission, with and with-out additive, and intentionally adulteratedhydrated ethanol for standard emission, withand without additive.

Sampling

A full-flow dilution tunnel and a critical-flow Venturi constant-volume sampler (HoribaCFV-CVS model 20A) system were used to col-lect vehicle exhaust gases. Before collection,the gases were mixed with filtered ambient air.The filter set was composed of a particle filter,an activated carbon filter, and an absolute par-ticle filter. Particle emissions were collectedusing a Mini-Vol air sampler (Airmetrics,Eugene, OR). The particulate matter (PM)passed through a particle size separator andthe fine and coarse fractions were selected byinertial impaction. The PM mass was deter-mined gravimetrically by the weight differenceof the filters before and after sampling. Beforeweighing, the filters were stabilized in an accli-matized environment for approximately 48 h,at a temperature between 20 and 30°C withhumidity between 25 and 40%, and subse-quently submitted to an americium (Am) radia-tion source to neutralize electrical charges.

The elemental composition of the sampleswas determined by means of the PIXE (particleinduced x-ray emission) method in the Labora-tory of Material Analysis by Ionic Beam, withthe collaboration of the Institute of Physics ofthe University of Sao Paulo. The software

WinQXAS (quantitative x-ray analysis systemfor MS Windows operating systems) was usedto analyze the x-ray spectra. Blank sampleswere used to account for the elements inher-ent to the filter production process. A clusteranalysis (Ward’s method using Euclidean dis-tance) was performed to find associationsbetween data sets.

RESULTS AND DISCUSSION

Particulate Matter Emissions

Emission rates of particulate matter (PM10)from the ethanol vehicle were approximatelythreefold less than the average emission fromthe gasohol vehicle. For the ethanol vehicle,PM10 emission rates were between 1.2 and3 mg/km, whereas for the gasohol vehicle theyranged between 2.49 and 11.83 mg/km. Theaverage emission rate of fine fraction (da <2.5 μm) was roughly twice as much as theaverage emission rate of coarse fraction(2.5 μm < da < 10 μm). The values for fineand coarse fractions were, respectively,4.35 mg/km and 1.96 mg/km for the gasoholvehicle, and 1.41 mg/km and 0.8 mg/km,respectively, for the ethanol vehicle.

In a study conducted by Geller et al.(2006), PM10 emissions from gasoline-poweredvehicles were noted to be between 5.5 and6 mg/km, the same order of magnitude as thevalues found in this research. The most signifi-cant difference between results occurs with astudy performed in the Jânio Quadros (JQ) tun-nel, São Paulo, by Sánchez-Ccoyllo et al.(2008), who reported an emission rate of PM10from light-duty vehicles (gasohol and ethanol

TABLE 1. Vehicle Specification

Vehicle

Vehicle characteristics

Type Year Engine MassMileage accumulated

1 Gasohol light-duty passenger vehicle

1998 1.8L displacement 1111 kg 67500 km78 kW at 5500 rpm15.1 kgm at 4500 rpm

2 Flex-fuel light-duty utilitary vehicle

2004 1.8L displacement 1111 kg 56500 km73 kW at 5700 rpm14.4 kgm at 3000 rpm

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904 M. FERREIRA DA SILVA ET AL.

vehicles) of 197 mg/km, approximately 32-foldgreater than values obtained in the present study.

Elemental Composition

Trace elements and metals in the exhaustemissions of the gasohol and ethanol vehiclesare presented individually in Figure 1. The ele-ments Fe, S, and Al were the most abundant,followed by Ca, Si, Br, and Zn. The gasoholvehicle emission profile was similar to thatobtained by others (Cadle et al., 1997; Geller etal., 2006), where the crust metals (Al and Fe)were among the trace elements of higher con-centration in the exhaust of the vehicles tested.Zinc in both types of vehicles was quantitativelysimilar to the emission rates of crust metals.

The sulfur emission rate in the exhaust ofthe gasohol vehicle was 66.75 μg/km. Theoccurrence of sulfur in gasoline was presumeddue to its presence in crude oil. Consideringthat ethanol fuel is obtained by distillation ofsugar cane juice, significant amounts of sulfurin the ethanol emissions were not expected.However, in the exhaust of the ethanol vehi-cle, a sulfur concentration of 24.73 μg/km wasobserved. This elevated concentration is prob-ably due to the presence of sulfates in thewater used for hydration of the ethanol and tothe use of fuel additives and lubricants in etha-nol vehicles to compensate for the reducedlubricant power of this fuel. Other elements,such as K, Ca, and Br, may originate fromlubricants and additives and may account for

the higher elemental concentration in the eth-anol vehicle.

Gasohol Vehicle Results

The degree of association between differentmetal elements was determined by using theWard method (minimum variance method)combined with the Euclidean distance measure.The result of the cluster analysis is presented asa tree for visual classification of similarity, calleda dendrogram. Figure 2 is the representation ofthe dendrogram of the metals collected in theexhaust of the gasohol vehicle.

First Group: Mn, Pt, Ni, Cu, Pb, Cr, andZn These metals were found in relatively lowconcentrations, suggesting that their presence

FIGURE 1. Elements identified in the exhaust of both gasohol and ethanol powered vehicles.

FIGURE 2. Dendrogram of variables obtained by the method ofward. metals collected in the exhaust of the gasohol poweredvehicle.

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was probably due to impurities in the fueland lubricant. Copper is added as an antiox-idant and may be present in the coarse frac-tion of the particles, originating from thewearing down of the engine bearings orother components. The presence of Zn isassociated with the use of additives andlubricants. Zinc dithiophosphate is com-monly added to engine oils for its antiwear-ing and antioxidant properties (Cadle et al.,1997) and was among the most abundantelements present in fine tailpipe emissions ofgasoline cars (Morawska & Zhang, 2002).

Some elements, such as Pb and Pt, arefound in fuels and lubricant additives. More-over, Pt may also be generated by catalyticconverters. Artelt et al. (1999a) and Zereini etal. (2000) found low emissions of this elementfrom catalytic converters of in-use vehicles,which is due to the tendency of this emissionto decrease over time. The average Pt concen-tration determined in this study was 67.5 ng/km.Artelt et al. (1999b) reported concentrations aslow as 9 and as high as 18 ng/km; Palacioset al. (2000) obtained 100 ng/km; Moldovanet al. (2002) found values between 27 and313 ng/km; and Ravindra et al. (2004) found10.2 ng/km.

Second Group: Al The origin of the Al isprobably due to the use of modern catalyticconverters, whose substrate consists of Al andmagnesium silicate (2MgO·2Al3O·5SiO3),coated with Al2O3, and released by abrasion.Kitto et al. (1992) noted a similar finding.

Third Group: Fe Graphically isolatedfrom all the other metals, Fe represented about72% of the total metal emission rate. This highpercentage is due to its presence in com-position of fuels and probably to the internalcorrosion of the engine and ducts. During theassays, the presence of coarse particles of Feproduced by the corrosion process wasobserved in the polycarbonate filter.

Ethanol Vehicle Results

Figure 3 is the representation of the den-drogram of the metals collected in the exhaustof the ethanol vehicle. The profile of emissionsof ethanol-powered vehicles was similar to that

of gasohol-powered vehicles, but in lower con-centrations.

First Group: Mn, Pt, Ni, Cu, Pb, Cr, Zn,and Al After subtraction of blanks, the analy-sis found low concentrations of these elementsin ethanol emissions. The metals Mn, Pt, andZn were present in only one of four samples.Zinc is usually associated with contaminationsduring fuel production, storage, or transport.The presence of some metals may beexplained by the use of lubricants and also bythe absorption of micronutrients in the soil bysugar cane. Silva et al. (2007) conducted astudy related to the transfer of heavy metals insoil to sugar cane from fertilization with urbanwaste compost and found that the mosttroublesome metal is Ni, followed by Cd andCu. Lead decay was faster in the soil due tostrong interaction with iron oxides, aluminum,and clay.

Second Group: Fe The concentration ofthis metal was responsible for approximately92% of the total of metal particles. Similarly toZn, Fe contamination is likely to occur duringthe production, storage, or transportation ofethanol. Teixeira et al. (2005) suggested thatcorrosion problems are more severe withalcohol than with other hydrocarbon fuels dueto its chemical composition. The presence ofCu and Fe may also be associated with enginecorrosion.

FIGURE 3. Dendrogram of variables obtained by the method ofward. metals collected in the exhaust of the ethanol poweredvehicle.

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906 M. FERREIRA DA SILVA ET AL.

Emission Comparison

Figure 4 shows the degree of correlationbetween emission rates of the elementsmeasured in the exhaust of gasohol- andethanol-powered vehicles (R2 = .85). It wasobserved that, despite the existing correlation,the ethanol vehicle emitted much less than thegasohol vehicle.

Figure 5 compares fine and coarse frac-tions collected in the exhaust of gasohol andethanol vehicles. It is noteworthy that in bothcases the emission of fine particles is higherthan the emission of coarse particles. In the

gasohol emissions, the metals Fe, Zn, Cu, Ni,Pb, and Mn are predominantly in the coarsefraction, whereas in the ethanol emissions, Fe,Al, Ni, Cu, Zn, Pb, and Pt are mostly in the finefraction. This observation in the ethanol emis-sions is a basis for concern because of thesmaller the aerodynamic diameter, the greateris the chance of being deposited in the alveoliand thus penetrating into the internal organ-ism. Some water-soluble compounds (sulfates,nitrates, and some metals) may also be dis-solved in the aqueous fluid of the alveolar sur-face and cross the alveolar barrier and reachthe circulation (Pope et al., 2002; Saldivaet al., 2002; Pope & Dockery, 2006). Notethat the metal deposition into lower airways,especially Fe, found in larger quantities trig-gered the generation of toxic oxygen free radi-cals and produced acute and chronic lunginjury (Valavanidis et al., 2000).

Table 2 demonstrates a comparisonbetween the average emission rates of traceelements found by Sánchez-Ccoyllo et al.(2008), Geller et al. (2006), and the presentstudy. In all these studies, the metal Fe had thehighest emission rates. Emission rates obtainedby Sánchez-Ccoyllo et al. (2008) were the high-est among the three sets of data. In particular,

FIGURE 4. Linear relationships between emission rates of traceelements measured in gasohol powered vehicles versus ethanolpowered vehicles.

FIGURE 5. Distribution of metals in mass per distance in the exhaust of gasohol and ethanol powered vehicle.

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METAL EMISSION FROM GASOLINE AND ETHANOL CARS 907

Fe showed values about 43-fold higher thanstudies performed with dynamometer tests.The difference between the three sets of datamay be attributed to the following factors: dif-ferences in vehicle type and age, road condi-tions, fuel composition and consumption, andweather, as well as the deterioration of emis-sion control components that affect the charac-teristics and chemistry of vehicle emissions(Chellan et al., 2005).

CONCLUSIONS

Data showed that the ethanol-poweredvehicle emitted three times less particles com-pared to the gasohol vehicle. The lower parti-cle emission in the ethanol-powered vehiclewas mainly due to fuel characteristics, such aschemical composition and better combustionefficiency. To ensure the safety of biofuels (eth-anol), however, this phenomenon needs moreinvestigation and other specific factors takeninto consideration. The higher release of finePM into the atmosphere must be consideredan important aggravating factor. Although

evidence indicates that exposure to fine-parti-cle atmospheric produces adverse health out-comes, Brazilian legislation for light-dutyvehicles does not regulate these emissions.Platinum emission rates obtained from thegasohol-powered vehicle were of the samemagnitude as those found globally. Despitebeing generated by automotive catalytic con-verters, the presence of the noble metals Pdand Rh was not identified. Iron was the metalfound in more significant concentrations inboth ethanol and gasohol vehicles. Results sug-gest the need for preventive control of particlesgenerated by light-duty vehicles, due to theirpotential risk not only to human health, butalso to the environment.

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TABLE 2. Comparison of Average Emission Rates µg.km−1

Elements

Sánchez-Ccoyllo et al. (2008)

Geller et al. (2006) Present study Present study

Vehicular emissionsJQ tunnel

Gasoline emissionsDynamometer tests

Gasohol emissionsDynamometer tests

Ethanol emissionsDynamometer tests

PM (mg km−1) 197.0 5.8 6.3 2.2A1 1036.0 2.3 48.7 1,8Si 118.3 NI 19,9 21,0P NI NI 9,9 6,1S 465.7 8.7 66,8 24,5C1 NI NI 1,1 0,0K NI 1.9 3,8 5,5Ca NI 18.3 22,5 23,9Cr NI 0.1 1,6 0,5Mn 96.3 0.2 1,1 0,2Fe 7762.0 10.3 181,0 83,1Ni 2.4 0.1 2,1 1,8Cu 261.0 1.8 3,7 0,8Zn 167.4 4.7 10,8 1,0Br 220.0 NI 14,5 23,3Pt NI NI 0,1 0,0Pb 14.1 0.2 3,5 0,6

NI: Not informed.

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