Energy & Fuels 2007, 21, 2731-2736

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Nonregulated Pollutants Emitted from Euro 3 Diesel Vehicles as a Function of Their Mileage
George Bikas, and Efthimios Zervas*,
Institut fu r Technische Mechanik, Templergraben 64, 52056 Aachen, Germany, and Department of EnVironmental Engineering, Democritus UniVersity of Thrace, Vas. Sofias 12, 67100 Xanthi, Greece ReceiVed January 22, 2007. ReVised Manuscript ReceiVed May 23, 2007

The impact of mileage, from 4000 to 96 000 km, on the exhaust emissions of several nonregulated pollutants is studied in the case of several Euro 3 diesel passenger cars, tested on the New European Driving Cycle. The results show that the emissions of the four regulated pollutants remain within the regulatory limits. Exhaust NOx and particulate matter remain constant with mileage, while the emissions of hydrocarbons and CO increase, because of a partial deactivation of the oxidation catalyst. Exhaust emissions of many nonregulated pollutants are not particularly affected by the partial deactivation of the catalyst. Exhaust concentrations of methane, 1,3-butadiene, benzene, the main carbonyl compounds, and particulate sulfates remain constant. However, the exhaust concentrations of some other nonregulated pollutants, such as exhaust olefins, heavy HCs, heavy carbonyl compounds, and light polycyclic aromatic hydrocarbons (PAHs) increase. The emissions of heavier PAHs and N2O decrease with mileage.

Introduction CO, hydrocarbons (HCs), NOx, and particulate matter (PM) emissions of diesel passenger cars are regulated in terms of mass emitted per distance driven on a regulated driving cycle. Driving cycles have been derived to account for real life driving conditions and are used for homologation purposes. Because driving conditions differ from country to country or between continents, each region has its own driving cycles. The official European driving cycle is called New European Driving Cycle (NEDC),1 but other cycles are used in the U.S.A. or Japan to characterize the local conditions. Each passenger car must respect the exhaust emissions limits for a certain mileage, depending upon the regulation in use. In the European Union, the Euro 3 emission norm for passenger cars was introduced in the year 2000 and was valid until the year 2005, when it was replaced by the more stringent Euro 4 regulation. However, exhaust emissions also contain nonregulated pollutants, which are not subject of the introduced emission norms. Among diesel nonregulated pollutants, several authors study the emission of individual HCs2-4 and especially those of methane, a gas with a strong greenhouse effect. However, the total contribution of passenger cars to global methane emissions is estimated to be very low, not more than 0.3-0.4%5 of the total methane emissions.
* To whom correspondence should be addressed. Telephone: +3024510-79392. E-mail: ezervas@env.duth.gr. Institut fu r Technische Mechanik. Present address: HMETC-Hyundai-Platz 1, 65428 Ru sselsheim, Germany. Democritus University of Thrace. (1) Directive 70/220. www.europa.eu.int. (2) Zervas, E.; Montagne, X.; Lahaye, J. Atmos. EnViron. 2001, 35, 1301-1306. (3) Schmitz, T.; Hassel, D.; Weber, F. J. Atmos. EnViron. 2000, 34, 4639-4647. (4) Graham, L. Atmos. EnViron. 2005, 39, 2385-2398. (5) Nam, E. K.; Jensen, T. E.; Wallington, T. J. EnViron. Sci. Technol. 2004, 38, 2005-2010.

N2O is a nonregulated exhaust pollutant with a very strong greenhouse effect, which is about 300 times higher than this of CO2.6 Its lifetime in the atmosphere is estimated to be 170 years.7 The contribution of passenger cars to total N2O emissions is estimated to 6-32% of the total N2O emissions, depending upon the author.7-9 Another family of diesel nonregulated pollutants is carbonyl compounds, which are emitted not only because of incomplete combustion but also because of the oxidation of HCs on the oxidation catalyst. Some authors study the emission of carbonyl compounds at some specific engine points2,10 or on driving cycles other than NEDC.3,4,11 The first two carbonyl compounds, formaldehyde and acetaldehyde, are considered as toxic pollutants. A particular family of pollutants is polycyclic aromatic hydrocarbons (PAHs). PAHs are emitted in extremely low concentrations; however, some of them are suspected to be toxic. PAHs are also measured in the exhaust gas of diesel vehicles.12 It must be noted that the major part of PAHs is formed during combustion and not from fuel PAHs.13 Even if several authors study the emission of the above pollutants, there is no study today reporting the impact of vehicle mileage on their exhaust emissions. In this study, several passenger cars equipped with a Euro 3 diesel engine, are used
(6) Huai, T.; Durbin, T. D.; Miller, J. W.; Norbeck, J. M. Atmos. EnViron. 2004, 38, 6621-6629. (7) Karlsson, H. L. Sci. Total EnViron. 2004, 334, 125-132. (8) Becker, K. H.; Lorzer, J. C.; Kurtenback, R.; Wiesen, P. EnViron. Sci. Technol. 1999, 33, 4134-4139. (9) Becker, K. H.; Lorzer, J. C.; Kurtenbach, R.; Wiesen, P.; Jensen, T. E.; Wallington, T. J. Chemosphere: Global Change Sci. 2000, 2, 387395. (10) Cardone, M.; Prati, M. V.; Rocco, V.; Seggiani, M.; Senatore, A.; Avitolo, S. EnViron. Sci. Technol. 2002, 36, 4656-4662. (11) De Abrantes, R.; De Assuncao, J. V.; Hrai, E. Y. ReV. Saude Publica 2005, 39, 1-6. (12) Lin, Y. C.; Lee, W. J.; Wu, T. S.; Wang, C. T. Fuel 2006, 85, 25162523. (13) Rhead, M. M.; Hardy, S. A. Fuel 2003, 82, 385-393.

10.1021/ef070036d CCC: $37.00 2007 American Chemical Society Published on Web 07/25/2007

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Figure 1. Emissions of regulated pollutants as a function of the mileage for the same (in the case of NEDC, ECE, and EUDC) or different vehicles (in the case of NEDC) tested. PM emissions are not analyzed in the case of different passenger cars in use.

to study the emissions of regulated and several nonregulated pollutants, such as individual HCs, methane, carbonyl compounds, PAHs, N2O, and sulfates, as a function of the mileage (or aging) from 4000 to 96 000 km. Experimental Section
Two types of aging were used at this study. The first type was based on tests on the same vehicle, equipped with a Euro 3, 1.9 L diesel engine, at three different mileages. This passenger car was tested at 4000, 30 000, and 75 000 km. The second type of aging was based on the analysis of different vehicles in use having different mileages, from 4000 to 96 000 km. All of these passenger cars were equipped with the same Euro 3, 1.9 L diesel engine. All passenger cars were tested on the NEDC using the official European regulations.1 For the first vehicle, the analyzed pollutants were regulated pollutants (CO, NOx, HCs, and PM) and nonregulated pollutants, such as individual HCs, carbonyl compounds, PAHs, N2O, and particulate sulfates. The second type of aging (tests on different passenger cars in use) was focused on the emissions of the four regulated pollutants, methane, and N2O. The four regulated pollutants were analyzed according to the official European regulations.1 Individual HCs were analyzed by gas chromatography using flame ionization detector (GC/FID). Carbonyl compounds were collected in a 2,4-dinitrophenylhydrazine (DNPH) solution in acetonitrile, and the final solution was analyzed by high-performance liquid chromatography using ultraviolet detection (HPLC/UV). N2O was analyzed by gas chromatography using electron capture detection (GC/ECD). The soluble organic fraction (SOF) was extracted from PM, and PAHs were analyzed using highperformance liquid chromatography (HPLC) with fluorescence detection, while particulate sulfates were analyzed using ionic chromatography (IC) with conductometric detection.

Figure 1, where it can be seen that NOx and PM emissions remain particularly constant with mileage. The results of the tests on the same vehicle at three different mileages show that this stability is observed not only on the NEDC but also on the two parts of this driving cycle, ECE (urban part) and EUDC (extra-urban part). The results of different vehicles with different mileages show a quite remarkable stability of NOx emissions because exhaust NOx emissions are on average 0.33 g/km ( 9.7%. Because NOx and PM are only engine-out pollutant emissions and there is no after-treatment to treat them, this statement indicates that engine aging does not have an effect on these emissions. Another author12 reports than NOx emissions decrease at 18 000 km, while PM emissions remain constant, compared to the same vehicle at 0 km. Contrary to NOx and PM emissions, HC and CO emissions increase about 40% from 4000 to 75 000 km in the case of the first vehicle; however, they remain within the regulatory limits. Lin et al.12 also reports an increase of these emissions from 0 to 18 000 km. In our case, a higher increase is observed on the EUDC than the ECE: 40 and 30% increase in the case of HCs and CO, respectively, in the case of the ECE, and 90 and 240% in the case of the EUDC. This is explained from a partial deactivation of the oxidation catalyst at 75 000 km. In the case of a fresh oxidation catalyst, even if engine-out HC and CO emissions are higher on the EUDC than the ECE, a higher exhaust gas temperature of the EUDC helps to oxidize the major parts of them. Consequently, a small deactivation of the catalyst leads to a relatively higher increase of these emissions on the EUDC than the ECE. The above trends are also confirmed from the results of different vehicles. Emission of Individual HCs. The exhaust of individual HCs was also analyzed. It must be noted that there is always a difference between the sum of all individual HCs measured by

Results and Discussion Emission of Regulated Pollutants. The emissions of regulated pollutants as a function of the mileage are shown in

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Figure 2. (Lower curves) Ratio of the sum of individual HCs measured by GC/FID over the total HCs measured by FID as a function of the mileage, for the entire NEDC and also for the ECE and EUDC. (Upper curves) Ratio of the sum of carbonyl compounds measured over the total HCs as a function of the mileage, for the entire NEDC and also for the ECE and EUDC.

GC/FID and the total HCs measured by FID,14 because a part of the HCs with a high molecular weight remains at the transfer lines and cannot be analyzed by GC/FID. Figure 2 shows that the ratio of the sum of all individual HCs measured by GC/ FID, over total HCs measured by FID, as a function of the mileage and part of the driving cycle (entire NEDC, ECE, and EUDC), varies from 0.3 to 0.75. Because heavier HCs are oxidized easier than lighter ones,15 a partial deactivation of the oxidation catalyst increases their percentage in total HCs. Because the oxidation catalyst is partially deactivated with mileage, the ratio of the sum of individual HCs measured by GC/FID over total HCs measured by FID decreases too. For the above reasons, the percentages of individual HCs may show some variations. The impact of mileage on the exhaust concentration of individual HCs is shown in Figure 3. In the case of one vehicle, methane, 1,3-butadiene, and benzene exhaust emissions are particularly constant as a function of the mileage not only for the entire NEDC but also for the ECE and EUDC. The stability of methane emissions is also confirmed from the results of different vehicles (Figure 4). The first vehicle emits about 8 mg/km of methane on NEDC for the three mileages tested (Figure 3), while all other vehicles emit on average 7.45 mg/ km, with a relative standard deviation of only 10.2% (Figure 4). Another study, using older vehicles on American driving cycles, reported the value of 13 ( 5mg/km.5 Except olefins, there is no clear tendency for an increase of the exhaust concentration of each family of exhaust HCs. This statement indicates that a part of the increase of the total HC emissions comes from the increase of olefin emissions and the other part comes from the increase of the emissions of heavier HCs, which are not analyzed by GC/FID. The percentages of three main unburned HCs, methane, 1,3butadiene, and benzene, as well as the major families of HCs,
(14) Zervas, E. Ph.D. Thesis, University of Mulhouse, France, 1996. (15) Meziere, I.; Castagna, F.; Prigent, M.; Pentenero, A. SAE Technical Paper Series 950932, 1995.

Figure 3. Exhaust emissions of individual HCs as a function of the mileage, at the NEDC, ECE, and EUDC.

relative to the total amount of HCs measured by FID, as a function of the mileage, are shown in Figure 5. Methane is the major HC, corresponding to about 7-12% of the total HCs, while 1,3-butadiene and benzene correspond respectively to about 1-1.8 and 2-3%. The percentages of methane and 1,3butadiene are lower than the percentages reported in a previous study, where only one operation point of an older diesel engine was used.2 The percentage of benzene is quite similar to the percentage reported in previous studies,2 indicating that probably the formation mechanism of this pollutant is quite independent of engine technology. With respect to not only the entire NEDC but also ECE and EUDC, one can observe that the percentage of the above-mentioned three HCs decreases as a function of the mileage, because of the partial deactivation of the oxidation catalyst, which has as a consequence an increase of the heavier HC emission. Because all other HCs are more easily oxidized under the increased temperature of the EUDC, the percentage of methane increases at this part of the cycle comparing NEDC and ECE, especially in the case of a fresh oxidation catalyst. Olefins are the major family of exhaust HCs corresponding to 30-40% of the total HCs, followed by alkynes (2.5-5%), aromatics (1.5-3%), alkanes (1.3-3%), and finaly isoalkanes (0.4-0.8%). Schmitz et al.,3 using older technology vehicles on U.S. Federal Test Procedure (FTP) and Autobahn driving cycles, found 11-13% alkanes, 55-65% alkenes, 12-14% alkynes, and 11-13% aromatics. As in the case of the previous HCs, the percentages of these families of HCs generally decrease with mileage because of the increase of heavy HCs measured by FID but not by GC/FID. Emission of Carbonyl Compounds. A total of 13 carbonyl compounds were detected in the exhaust gas: formaldehyde,

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Figure 4. (Lower curves) Exhaust emissions of CH4 and N2O as a function of the mileage, for different vehicles used (on the NEDC). (Upper curves) Exhaust emissions of N2O and SO42- as a function of the mileage, for one vehicle tested (on the NEDC, ECE, and EUDC).

acetaldehyde, acroleine, acetone, propionaldehyde, crotonaldehyde, methacroleine, MEC plus butyraldehyde, benzaldehyde, n-valeraldehyde, m-toluenaldehyde, and hexanaldehyde, at exhaust concentrations from 0.02 to 12 mg/km. Isovaleraldehyde, o-toluenaldehyde, and p-toluenaldehyde exhaust concentrations were below detection limits. The emission of the carbonyl compounds detected as a function of the mileage is shown in Figure 6. Formaldehyde and acetaldehyde are the two major exhaust carbonyl compounds.2,11 Figure 6 clearly shows that the emissions of lighter carbonyl compounds (formaldehyde, acetaldehyde, acroleine, acetone, and propionaldehyde) remain constant from 4000 to 75 000 km. The exhaust concentrations of heavier carbonyl compounds, as crotonaldehyde, mathacroleine, MEC plus butyraldehyde, benzaldehyde, n-valeraldehyde, m-toluenaldehyde, and hexanaldehyde, show an increase of 2-10 times, because of the partial deactivation of the oxidation catalyst. However, the exhaust concentration of these compounds on NEDC is quite low, from 0.1 to 0.8 mg/km, in the case of 75 000 km. The exhaust concentrations of all carbonyl compounds are quite low at the EUDC (the exhaust concentration of most heavy carbonyl compounds are at the detection limits) and lower than at the ECE. The increased exhaust temperature and thus the higher performance of the oxidation catalyst is one reason for that. On the other hand, the shifting of the operation points toward a higher speed and load during this driving mode causes a change in the level and distribution of the raw emissions, as the combustion efficiency increases. The exhaust concentration of almost all carbonyl compounds increases 40-50% at the EUDC with mileage because of the partial deactivation of the oxidation catalyst; however, this increase is very low compared to the total emissions. The percentage of each carbonyl compounds is shown in Figure 7. Formaldehyde is the major carbonyl compound;2,11

Figure 5. Percentage of individual HCs over the total HCs as a function of the mileage, at the NEDC, ECE, and EUDC.

its percentage is 51-56% on the NEDC. This percentage is quite similar to the percentage reported in a previous study using an older diesel engine operating on only one specific point,2 indicating that the mechanisms of carbonyl compound formation must be quite independent of the engine technology. Generally, the formaldehyde percentage decreases very slightly with mileage and is slightly higher at the EUDC than the ECE. Acetaldehyde is the second carbonyl compound,2,11 with a percentage corresponding to 25-30% of the total carbonyls on the NEDC, following by acetone (7-10%), propionaldehyde (4%), MEC plus butyraldehdye (1-3%), benzaldehyde (0.71.2%), methacroleine (0.3-1%), and crotonaldehyde (0.1-1%), while the other carbonyl compounds correspond to less than 0.5% each. Except formaldehyde, there is no clear trend concerning the percentages of carbonyl compounds at the EUDC and ECE and their percentage as a function of the mileage. A previous study11 reports that, for different vehicles tested on FTP, the ratio of formaldehyde/acetaldehyde always remains constant and around 7/3 or 2.33. In our case, the ratio of formaldehyde/acetaldehyde is from 1.7 to 2.8. The same study reports 43 ( 34 mg/km of formaldehyde, 15 ( 13 mg/km of acetaldehyde, and 58 ( 47 mg/km of the total carbonyl compounds, however, using microbuses of older technology measured on the FTP driving cycle. The exhaust concentration of the total carbonyl compounds corresponds to about 20-40% of the total HC exhaust concentration (Figure 2). This percentage decreases with mileage because of the increased exhaust emissions of HCs as a result of the partial deactivated oxidation catalyst. For the same reason,

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Figure 6. Exhaust emissions of carbonyl compounds as a function of the mileage, at the NEDC, ECE, and EUDC.

this percentage is lower at the EUDC than the ECE. This percentage is quite similar to the percentage reported in a previous study using an older diesel engine operating in one specific point.2 Another study3 reports that carbonyl compounds correspond to 30-70% of the total HCs when older technology vehicles were used on FTP and Autobahn driving cycles. Emission of PAHs. The emissions of PAHs are shown in Figure 8. Because of technical reasons, no PAH analysis is performed at the point of 30 000 km. It must be noted that the measurement uncertainties are about 40% and most of the changes presented here are within this variation. Total PAH emissions are quite independent of the mileage (8 g/km at 4000 km and 9 g/km at 75 000 km). The exhaust concentrations found here are lower than the values reported in another study.16 Another author12 reports that total PAH emissions decrease with the mileage. The main PAHs are fluoranthene (corresponding to about 2932% of the total PAHs), pyrene (about 18-24%), and benzo(e)pyrene (about 11-12%). Figure 8 shows two tendencies about the PAH concentration: that of heavier PAHs, which generally remain constant or decrease with the mileage, and that of lighter PAHs, which increase. This last result is apparently due to the increased difficulty of the oxidation of lighter PAHs on the oxidation catalyst because its partial deactivation leads to an increase of their emissions. Heavier PAHs are more easily oxidized, and a partial deactivation of the oxidation catalyst does not influence their emissions. Emission of N2O. The emissions of N2O as a function of the mileage are shown in Figure 4. In the case of one vehicle,
(16) Geller, M. D.; Ntziachristos, L.; Mamakos, A.; Samaras, Z.; Schmitz, D. A.; Froines, J. R.; Sioutas, C. Atmos. EnViron. 2006, 40, 6988-7004.

Figure 7. Percentage of each carbonyl compound as a function of the mileage, at the NEDC, ECE, and EUDC.

the N2O emission is 16 g/km on the NEDC at 4000 km and decreases with the mileage to reach 8 g/km at 75 000 km. Other studies, using American driving cycles,8,9 also report similar values. N2O emissions from vehicles of newer technology are generally lower.17 N2O is formed on catalytic converters6,7,17 and preferably at low temperatures, where catalytic activity is low, and for this reason, N2O emissions are higher at a cold start than a hot start.17 For this reason, the N2O emissions decrease as a function of the mileage because of the partial deactivation of the oxidation catalyst. The emissions of N2O using several vehicles confirm this trend (lower curves in Figure 4). Because catalytic activity is higher on the EUDC than the ECE as a result of an increased temperature, N2O emissions should be lower at this part of the driving cycle. However, the opposite trend is observed; N2O is higher on the EUDC than the ECE. This is apparently due to higher NOx emissions of the EUDC. It must be noted that there is no evident correlation between NOx and N2O emissions or between N2O emissions and the temperature of the oxidation catalyst. Emission of Particulate Sulfates. The emissions of particulate sulfates on the NEDC are very low, about 1.3-1.5 g/km (Figure 4), and remain constant as a function of the mileage, indicating that the partial oxidation of the catalyst does not
(17) Lipman, T. E.; Delucchi, M. A. Clim. Change 2002, 53, 477516.

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Figure 8. Exhaust emissions of PAHs as a function of the mileage, at the NEDC.

influence them. The percentage of sulfates on the mass of collected particles is 3% (another author reports 2%)18 and remains constant as a function of the mileage.
(18) Kirchstetter, T. W.; Harley, R. A.; Kreisberg, N. M.; Stolzenburg, M. R.; Hering, S. V. Atmos. EnViron. 1999, 33, 2955-2968.

Conclusions The emissions of regulated and several nonregulated pollutants are studied on the NEDC as a function of the mileage in the case of passenger cars equipped with a Euro 3 diesel engine. Two types of tests were used. The first is based on tests on the same vehicle, equipped with a Euro 3, 1.9 L diesel engine, at 4000, 30 000, and 75 000 km. The second one is based on tests of different vehicles in use, all equipped with the same engine as the previous vehicle, having different mileages from 4000 to 96 000 km. The target is to find out if some pollutants increase with mileage. The obtained results show that all four regulated pollutants remain within the regulatory limits in the case of new and aged engines. Exhaust NOx and PM emissions remain particularly constant with the mileage, and the emissions of new or aged engines are quite similar. It must be noticed that there is no after-treatment device for these two pollutants, and the aging of mechanical parts of the engine does not increase their exhaust emissions. Contrary to this, exhaust HC and CO emissions increase about 40% from 4000 to 75 000 km, because of the partial deactivation of the oxidation catalyst at increased mileages. The deactivation of the oxidation catalyst leads to an increase of exhaust olefins and heavier HCs with mileage, while exhaust emissions of methane, 1,3-butadiene, and benzene are not influenced. The partial deactivation of the exhaust catalyst leads to an increase of some nonregulated pollutants, such as some heavier and minor carbonyl compounds and some light PAHs. However, exhaust emissions of the main exhaust carbonyl compounds and total PAHs remain constant with mileage. Because N2O is formed on catalytic converters, its exhaust concentration decreases with mileage, as a result of the partial deactivation of the oxidation catalyst. The emissions of particulate sulfates are very low and independent of engine and oxidation catalyst aging.
EF070036D