Characterization of Emissions from Malfunctioning Vehicles Fueled with Oxygenated Gasotine- Ethanol (E-10) Fuel-Part II Fred Stump, Silvestre Tejada, and David Dropkin National Exposure Research Laboratory U. S. Environmental Protection Agency Research Triangle Park, NC 27711 Colleen Loomis and Christy Pack Clean Air Vehicle Technology Center, Inc. Research Triangle Park, NC 27709 ------- ABSTRACT A 1993 Ford Taurus and a 1995 Chevrolet Achieva were tested using three different fuels: (1) a winter grade (E-10) fuel containing 10% (vol.) 200 proof ethanol, (2) a winter grade (WG) fuel without any oxygen containing compounds, and (3) a summer grade (SG) fuel without oxygenates. Vehicle emissions were characterized at test temperatures of 75 ( SG fuet only), 20, 0, and -20 °F. The vehicles were tested under a mode in which the vehicles were tuned to manufacturers specifications (NM mode) and under two simulated malfunction modes: 1) the oxygen (02 mode) sensor was disconnected and 2) the exhaust gas recirculating valve (EGR mode) was disconnected and plugged. The malfunction modes were not tested simultaneously. The vehicles were tested on the Urban Dynamometer Driving Schedule (UDDS) of the Federal Test Procedure (FTP). Four IM240 test cycles were run after each of the UDDS tests and the exhaust particulate matter (PM2.5 and PM10), from the four IM240 driving cycles were collected on single filters. The gaseous emissions were collected and analyzed for total hydrocarbons, carbon monoxide, oxides of nitrogen, speciated (individual) hydrocarbons, speciated (individual) aldehydes, ethanol, methanol, 2-propanol, methyltertiaiybutyl (MTBE) ether, and ethyltertiarybutyl (ETBE) ether. Hydrocarbon emissions generally increased as test temperature decreased for both vehicles, fuels, and test modes. The E-10 fuel reduced some emissions and increased others, while disconnecting the 02 sensor increased emissions over the other two modes. The trend for carbon monoxide and oxides of nitrogen emissions showed a general increase in emission rates as the testing temperature decreased. When the 02 sensor was disabled, the trend showed increasing carbon monoxide emissions and when the EGR valve was disabled it was observed that the oxides of nitrogen emissions generally increased. The emissions of the toxic compounds benzene and 1,3-butadiene tended to increase as the testing temperature decreased. Disconnecting the 02 sensor generally increased the emissions of these toxic compounds when compared with the NM mode emissions. The E-10 fuel generally reduced both benzene and 1,3-butadiene emissions from both vehicles. The measured emissions of formaldehyde and acctaldchydc from the test vehicles show a general increase in emissions as test temperature decreased with both the base and E-10 fuels. The PM2.5 and PM10 particulate emission rates were comparable. The particulate emissions from both vehicles followed the HC emission trend and increased as the test temperature decreased. The E-10 fuel reduced particulate emissions from the Taurus at all test conditions with the exception of when testing at 20 °F in the EGR mode but the effect of the E- 10 fuel on Achieva PM2.5 were not well defined. The Taurus emitted more particulate matter than the Achieva at all test conditions except when tested in the NM mode with SG fuel. Both vehicles emitted more particulate matter when the 02 sensor was disconnected. ------- INTRODUCTION Motor vehicles emit large quantities of hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NOx). These emissions participitate in the atmospheric photochemical processes to form ozone and other oxidants. Motor vehicles also emit toxic compounds such as formaldehyde, acetaldehyde, benzene, 1,3-butadiene and particulate matter (PM2.5 and PM10) all of which are of major health concern. The 1990 Clean Air Act Amendment specify a reduction in these toxic emissions.1 This study characterized the emissions from two recent model light duty gasoline powered vehicles tested at ambient temperatures of 75, 20, 0, and -20 °F. The test vehicles were operated on a commercially available winter grade fuel (with and without ethanol) and a commercially available summer grade fuel; (1) the winter grade fuel contained 10% (vol.) 200 proof ethanol (E-10), (2) the winter grade fuel without any oxygenates, and (3) the summer grade fuel without any oxygen containing compounds. In addition, the two vehicle were tested, using the different fuels at different temperatures when 1) the 02 sensor was disconnected and 2) when the EGR valve was disconnected and plugged (malfunction modes). Particulate emissions are becoming of major concern due to their adverse affects on materials, visibility reduction, atmospheric reactivity, and human health. Recent epidemiological studies have indicated health concerns for one particulate matter emissions with an aerodynamic diameter of 10 or less.2,3 In this study, individual PM2.5 and PM10 filters were taken from each of the UDDS tests (duplicate tests at each condition). After the completion of each UDDS test, the particulate emissions from four IM240 driving cycles were collected on individual PM2.5 and PM10 filters. Currently there is little information regarding particulate emission rates from recent model in-use light-duty gasoline vehicles 4 and very few studies have been done on vehicles tested at malfunction conditions at various ambient temperatures. 3 ------- EXPERIMENTAL METHODS AND MATERIALS The test fuels, vehicles, facilities, and procedures are described in this section. Test Fuels The fuels used in this study were a summer grade fuel, a winter grade fuel containing no ethanol and the winter grade fuel splash blended with ethanol to contain 10 % ethanol by volume (E-10). These fuels were purchased locally and are representative of the fuel in-use. The characteristics of the test fuels are listed in Table 1. Table 1. Characteristics of test fuels." Fuel Property Summer Winter Wintcr-E-1Q Specific gravity, g/cm3 0.75 0.73 0.74 RVPa 6.87 12.15 12.62 Distillation, °F IBP 102.00 84.20 83.48 10% 133.00 104.00 107.60 50% 219.00 189.50 153.50 90% 351.00 338.00 334.40 End Point 421.00 411.80 415.40 Paraffins, % 45.43 54.53 48.69 Olefins, % 14.08 21,02 18.77 Aromatics, % . 40.23 23.99 21.43 Benzene, % 1.23 1.15 1.03 Ethanol, % 0.00 0.00 10.00 a Reid vapor pressure. 4 ------- Test Schedule/Conditions A single UDDS test was performed on each vehicle at 75 °F. Duplicate tests, on each vehicle, were performed at each of the three lower test temperatures and test conditions (Table 2). The vehicles were conditioned with each test fuel at each test condition before actually testing the vehicle for data collection. Table 2. Test Schedule/Conditions for 1995 Chevrolet Achieva and 1993 Ford Taurus vehicles. Description Summer Test Conditions Winter Test Conditions Driving Cycles: UDDS + 4 lM240's UDDS + 4 IM240's Test Temperatures: 75 °F 20, 0, -20 °F Duplicate Runs: Single test only Duplicate runs Fuel Type: Summer Fuel Winter Fuel Ethanol: No Ethanol With/Without Ethanol Malfunction Modes: 02 and EGR 02 and EGR Emissions Measured: Gaseous Emissions Particles Measured PM2.5 and PM10 Gaseous Emissions Particles Measured PM2.5 and PM10 Test Vehicles The vehicles used in this study were on-loan and are described in Table 2a. Table 2a, Vehicles tested.3 Vehicle Cyl. Vehicle Displaced Fuel Emission Miles Liters System System 3 1995 Chevrolet Achieva 6 67297 3.1 SFI EGR/TWC/02S 1993 Ford Taurus 6 113497 3.0 SFI EGR/TWC/02S a EGR=Exhaust Gas Recirculation TWC- Three Way Catalyst 02S-0xygen Sensor SFI~ Sequential Fuel Injection 5 ------- Test Facilities Vehicle road simulations were conducted on a Horiba Model CDC800/DMA915 computerized DC electric chassis dynamometer. The dynamometer was housed in a temperature controlled chamber capable of maintaining vehicle test temperatures from -20 to 110 °F (+/- 1% °F), Vehicle emissions were transferred from the vehicle tailpipe to a constant volume sampling (CVS) system through a 7.62-cm i.d. (3 inch) section of flexible stainless steel tubing heated to 230 °F. The CVS system, which dilutes the tailpipe emissions with charcoal-filtered room air, has been described previously.5 A heater has been added behind the dilution air filter to raise the tunnel dilution air temperature to 150 °F to prevent formaldehyde and other compound losses in the system.6 Test Procedures Testing was conducted as described in the Code of Federal Regulations (CFR) Title 407 using the Urban Dynamometer Driving Schedule of the Federal Test Procedure (FTP). The Inspection/Maintenance (IM240) test was designed to detect malfunctioning vehicles with advanced (computer-controlled) emission systems. The test was patterned after the first two major accelerations and decelerations of the FTP and has a maximum speed of 56.7 miles per hour and test duration of 240 seconds. At the beginning of the test week, the vehicle to be tested was pre-conditioned by driving the vehicle over the UDDS cycle with the test fuel, in the test mode, and at the test temperature to be used for data collection. The daily UDDS test served (as duplicates were run at all temperatures except 75 °F) as the pre-conditioning for the following days test. During the test week when the vehicle, fuel, temperature, or mode were to be changed, the vehicle would be conditioned in the afternoon after the daily test was over, by running a LA-4 cycle (phase one and phase two of the UDDS cycle) at the test conditions to be used the following day. After each UDDS test cycle was run, then four IM240s were run and the PM2.5 and PM10 particles and the gaseous emissions were collected. All four IM240 cycle particulate emissions were collected on single filters using both PM2.5 and PM10 Cyclones (University Research Glassware, Carrboro. NC) system. Vehicle emissions were measured at 75, 20, 0, and -20 *F for each of the UDDS driving cycles and IM240 cycles. The gaseous regulated emissions and particle data shown for the IM240 cycles are an average of the four tests. An integrated emissions sample was collected from the CVS system in a Tedlar bag for each UDDS test phase, which included an initial 124 second sample. Also, a background air sample was taken after the charcoal dilution air filter. The regulated emissions (THC, CO, and NOx) were measured with instruments connected to the CVS system and used for real-time sampling during the testing. Vehicle emissions characterized were speciated (individual) hydrocarbons (more than 250 compounds), speciated aldehydes (12 compounds), regulated gaseous emissions, alcohols, and ethers. Identification or structural formulas for more than 95% of the emitted HCs have been 6 ------- determined by established gas chromatographie-mass spectrometric (GC-MS) techniques. Supplementary regulated, unregulated, speciated HCs, speciated aldehydes, ethanol, methanol, 2-propanol, methyltertiarybutyl (MTBE) ether, and ethyltertiarybutyl (ETBE) ether data are available from the authors. Tailpipe Emissions The vehicle UDDS bag samples were analyzed for speciated hydrocarbons, and speciated alcohols and ethers by gas chromatography.8 Data were manually transferred to a PC where peak assignments were made and then the data were finally transferred to the Archived Mobile Source Emissions Data Base (AME) . The individual compounds were identified using a Lotus 1-2-3 program developed for identifying compounds in complex chromatograms.9 The concentrations of the regulated emissions were reported as g/mi and mg/mi for individual HCs, aldehydes, and alcohols and ethers. Aldehyde emissions were sampled from the CVS system through a heated (212 °F) stainless steel line and collected on silica gel cartridges coated with acidified 2,4- dinitrophenylhydrazine. A mass flow controller was used to regulate the sampling rate of the aldehydes in the exhaust stream at 1 L/tnin. The aldehydes were analyzed by previous described liquid chromatographic procedures.10 7 ------- Table 3. Vehicle UDDS tailpipe emission rates at 75 °F. Vehicle Achieva Taurus Mode No Malfunction 02 Sensor Disconnected EGR Disconnected No Malfunction 02 Sensor Disconnected EGR Disconnected Fuel Summer Grade Summer Grade THC, g/mi 0.37 4.45 0.17 0.35 0.41 0.34 CO, g/mi 4.61 34.14 3.12 2.08 4.74 4.04 NOx, g/mi 0.71 0.85 2.02 0.76 0.79 0.73 Ethanol, mg/mi <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Formaldehyde, mg/mi 3.80 4.18 2.74 13.83 5.92 6.78 Acetaldehyde, mg/mi 1.73 3.82 1.45 0.86 1.54 1.12 Total Aldehydes, mg/mi 8.29 17.10 5.88 16.65 9.95 10.27 Benzene, mg/mi 13.80 182.06 8.03 8.34 11.46 8.56 1,3-Butadiene, mg/mi 1.60 27.47 1.10 1.11 1.52 1.16 PM2.5, mg/mi 2.80 5.80 1.30 0.70 9.00 11.80 PM10, mg/mi 1.00 7.60 2.20 <0.01 8.80 8.50 8 ------- Table 4. Vehicle UDDS tailpipe emission rates at 20°F. Vehicle Achieva Taurus Mode No Malfunction 02 Sensor Disconnected EGR Disconnected No Malfunction 02 Sensor Disconnected EGR Disconnected Fuel Basef E-10* Base E-10 Base E-10 Base E-10 Base E-10 Base E-10 THC, g/mi 0.76 1.32 5.35 5.06 0.65 0.74 1.23 1.09 4.60 3.63 1.04 1.02 CO, g/mi 9.20 10.60 140.28 67.63 8.48 7.96 12.30 9.62 81.40 49.04 10.67 8.99 NOx, g/mi 0.98 1.05 0.60 0.22 1.55 1.32 0.76 0.58 0.96 0.65 0.86 0.78 Ethanol, mg/mi <0.01 <0.01 <0.01 58.82 0.29 0.14 0.61 7.09 0.85 9.96 <0.01 38.50 Formaldehyde, mg/mi 2.47 7.27 35.29 17.27 19.62 4.42 6.04 10.91 25.88 11.61 4.56 4.90 Acetaldehyde, mg/mi 1.98 10.41 22.31 98.10 2.58 7.69 2.86 9.95 24.28 72.44 2.52 9.84 Total Aldehydes, mg/mi 7.75 22.16 102.09 136.66 7.17 15.92 14.31 26.36 92.56 105.59 12.70 19.99 Benzene, mg/mi 14.89 45.44 143.12 166.65 18.50 20.22 40.57 29.33 160.37 132.03 31.34 30.45 1,3-Butadiene, mg/mi 1.71 5.41 26.61 24.68 2.63 3.00 6.51 4.58 40.24 25.31 5.35 5.04 PM2.5, mg/mi 11.90 12.85 23.80 18.90 9.60 NAa 41.25 28.80 58.80 33.40 23.40 27.00 PM10, mg/mi 11.60 12.60 28.00 20.90 11.60 NA NA NA NA NA NA NA f Winter grade, without ethanol f Winter grade, with ethanol a Data not available 9 ------- Table 5. Vehicle UDDS tailpipe emission rates at 0°F. Vehicle Achieva Taurus Mode No Malfunction 02 Sensor Disconnected EGR Disconnected No Malfunction 02 Sensor Disconnected EGR Disconnected Fuel Basef E-10 1 Base E-10 Base E-10 Base E-10 Base E-10 Base E-10 THC, g/mi 1.76 3.35 17.40 11.03 1.44 1.33 2.16 1.82 6.81 4.99 1.90 1.80 CO, g/mi 16.95 28.20 133.67 146.49 16.55 14.40 18.58 14.98 113.77 79.05 16.18 15.51 NOx, g/mi 1.10 0.87 0.15 0.25 1.60 1.61 0.82 0.70 0.87 0.91 1.04 0.81 Ethanol, mg/mi 0.30 254.75 0.45 123.92 0.32 0.53 <0.01 35.41 1.03 37.47 0.31 81.86 Formaldehyde, mg/mi 3.00 12.30 13.41 49.64 2.90 5.53 6.20 5.34 29.75 19.66 5.97 6.34 Acetaldehyde, mg/mi 2.35 31.04 19.67 247.96 2.78 12.63 3.48 15.38 20.68 101.50 3.76 12.99 Total Aldehydes, mg/mi 11.66 54.31 76.58 347.17 11.25 23.45 17.63 27.91 91.00 159.53 18.15 27.81 Benzene, mg/mi 52.31 99.53 510.02 126.42 41.45 41.30 72.51 67.71 207.85 174.95 63.95 60.72 1,3-Butadiene, mg/mi 5.40 .10.11 77.68 20.42 4.71 3.92 10.81 10.61 37.27 39.05 10.67 9.45 PM2.5, mg/mi 40.00 40.90 88.00 54.60 25.00 35.00 83.60 71.30 121.05 78.90 75.50 68.80 PM10, mg/mi 38.20 42.95 90.00 59.00 20.40 35.60 NAa NA 115.75 NA NA NA f Winter grade, without ethanol 1 Winter grade, with ethanol a Data not available 10 ------- Table 6. Vehicle UDDS tailpipe emission rates at -20°F. Vehicle Achieva Taurus Mode No Malfunction 02 Sensor Disconnected EGR Disconnected No Malfunction 02 Sensor Disconnected EGR Disconnected Fuel Basef E-10* Base E-10 Base E-10 Base E-10 Base E-10 Base E-10 THC, g/mi 3.55 2.85 12.31 4.01 2.61 2.41 3.79 3.10 10.42 6.92 3.81 2.99 CO, g/mi 25.65 21.06 154.34 139.34 21.14 18.58 23.40 29.40 163.54 94.82 21.72 26.34 NOx, g/mi 1.19 1.18 0.55 1.09 1.63 1.87 0.80 0.70 0.76 1.05 1.09 0.84 Ethanol, mg/mi 1.32 35.91 1.00 29.70 1.48 11.91 0.77 64.07 0.39 89.50 0.14 47.32 Formaldehyde, mg/mi 9.05 6.97 30.09 9.05 6.57 6.80 8.19 13.20 36.09 28.22 6.01 10.57 Acetaldehyde, mg/mi 4.32 23.64 33.84 38.16 2.98 18.96 4.30 25.21 28.37 123.27 4.38 24.50 Total Aldehydes, mg/mi 24.56 41.12 118.49 61.78 17.57 34.43 23.82 52.68 121.19 201.17 21.48 47.32 Benzene, mg/mi 115.59 96.71 357.37 139.34 83.64 67.94 116.79 109.05 303.94 232.39 112.66 115.04 1,3-Butadiene, mg/mi 13.64 9.93 74.82 13.02 12.15 7.07 12.73 16.23 47.59 51.08 15.46 16.49 PM2.5, mg/mi 80.20 81.45 121.15 80.70 41.65 78.40 150.85 146.20 194.50 169.20 141.47 119.90 PM10, mg/mi 87.55 87.55 124.70 87.60 46.05 84.95 144.30 NAa 201.30 NA 138.07 NA f Winter grade, without ethanol * Winter grade, with ethanol a Data not available 11 ------- Table 7. IM240 vehicle tailpipe emissions rates. Vehicle Achieva Taurus Mode No Malfunction 02 Sensor Disconnected EGR Disconnected No Malfunction 02 Sensor Disconnected EGR Disconnected Fuel Summer Grade Summer Grade Temperature 75°F THC, g/m 0.09 0.20 0.07 0.18 0.28 0.15 CO, g/mi 2.40 4.63 2.04 1.34 2.13 1.25 NOx, g/mi 0.82 1.56 2.80 0.92 1.48 0.89 PM2.5, mg/mi <0.01 1.40 <0.01 0.70 15.50 17.60 PM10, mg/mi 2.10 0.20 6.10 0.50 12.90 15.30 12 ------- Table 7a. IM240 vehicle tailpipe emissions rates. Vehicle Achieva Taurus Mode No Malfunction 02 Sensor Disconnected EGR Disconnected No Malfunction 02 Sensor Disconnected EGR Disconnected Fuel Base1 E-10' Base E-10 Base E-10 Base E-10 Base E-10 Base E-10 Temperature 20°F THC, g/m 0.24 1.44 4.34 5.31 0.13 0.17 0.40 0.19 2.98 2.34 0.18 0.16 CO, g/mi 4.36 11.26 133.28 85.18 4.16 3.52 3.38 1.70 62.46 36.56 1.74 1.49 NOx, g/mi 0.60 0.70 0.28 0.20 2.33 2.15 1.24 0.66 1.12 0.74 1.13 0.96 PM2.5, mg/mi 3.20 5.95 9.15 4.20 7.15 NAa 5.60 2.40 7.00 5.50 2.50 5.20 PM10, mg/mi 3.25 5.40 7.30 4.70 6.13 NA NA NA NA NA NA NA n Temperature 0.92 0°F THC, g/m 0.18 1.28 10.62 5.14 0.14 0.14 0.24 0.20 3.56 2.62 0.20 0.16 CO, g/mi 4.22 11.96 98.00 100.79 3.76 3.12 2.55 2.17 87.72 46.36 2.05 1.68 NOx, g/mi 0.76 0.82 0.12 0.19 2.49 2.22 0.98 0.76 1.07 1.00 1.14 0.96 PM2.5, mg/mi 8.20 1.85 28.73 2.30 4.55 4.35 8.00 9.60 9.90 10.00 8.40 5.60 PM10, mg/mi 4.70 4.70 26.63 6.30 4.25 6.35 6.00 NA 11.05 NA 7.20 NA Temperature -20°F THC, g/m 2.24 0.60 17.60 1.54 0.28 0.16 0.25 0.35 4.00 3.06 0.25 0.30 CO, g/mi 18.41 7.32 186.35 35.22 4.88 2.98 2.61 5.94 98.48 55.46 1.76 4.13 NOx, g/mi 0.79 0.88 0.06 . 0.44 2.38 2.66 0.99 0.88 1.22 1.34 1.14 1.05 PM2.5, mg/mi 7.65 3.34 85.00 1.65 6.65 5.05 8.10 13.70 12.00 14.90 11.20 13.40 PM10, mg/mi 10.45 5.05 84.40 1.65 3.75 7.50 6.35 NA 13.25 NA 8.17 NA f Winter grade, without ethanol * Winter grade, with ethanol a Data not available 13 ------- Results and Discussion Vehicle tests were performed in duplicate for all temperatures except at 75 °F. as only a single test with summer grade fuel was run. The data were not statistically evaluated since only single and duplicate tests were made and the comparisons should be viewed from this perspective. The THC emission results reported were the values determined by the analytical bench and total hydrocarbon analyzer (using the flame ionization detector) rather than a summation of the individual hydrocarbons as determined by gas chromatographic analysis. Tables 3-6 contain the UDDS tailpipe regulated, toxic, and particulate emission data and Tables 7 and 7a contain the 1M240 tailpipe gas phase and particulate emission data. Also, detailed hydrocarbon and aldehyde and ketone tables are included showing the compounds analyzed for from each bag sample taken from the FTP test. Figures 1 through 60 show the relation of compound emission rates for the vehicles, fuels, test cycles, and test modes at the program test temperatures. Each point of the plots displayed is an average of the vehicle tests at each test temperature. Figures 61 through 66 are regression plots (individual vehicle tests) showing the relationship of PM2.5 vs PM10 and THC vs PM2.5 emissions. Also, included are plots of THC vs ethanol and methanol emissions with both fuels. Regulated Emissions Total Hydrocarbons-UDDS Cycle. Hydrocarbon emissions (Figures 1-6) generally increased as test temperature decreased for both vehicles, fuels, and test modes. The vehicle's engine air/fuel mixture is controlled by a feedback loop via the oxygen sensor and when the sensor was disconnected, the vehicle operated in a slightly rich fuel condition throughout the test cycle. The Taurus emitted more HCs than the achieva when tested with the base fuel, NM mode, and the lower test temperatures (1.23 vs 0.76 g/mi at 20 UF. 2.16 vs 1.76 g/mi at 0 °F, and 3.79 vs 3.55 g/mi at -20 °F) but emissions were similar at 75 °F. Disconnecting the EGR reduced the HC emissions (compared to the NM modes emissions) from the Achieva (base fuel) and generally from the Taurus, under the NM mode, using the base fuel. Disconnecting the 02 sensor on the Taurus resulted in an increase of emissions from 0.35 to 0.41 g/mi (SG fuel at 75 °F) and a maximum increase of from 3.79 to 10.42 g/mi (base fuel at -20 °F). The Achieva emissions, with the 02 disconnected increased from 0.37 to 4.45 g/mi (SG fuel 75 °F) to a maximum increase of from 1.76 to 17.40 g/mi (base fuel at 0 °F). The H-10 fuel reduced emissions from the Taurus from 1.23 to 1.09 g/mi at 20°F, 2.16 to 1.82 g/mi at 0 °F, and 3.79 to 3.10 g/mi at -20 °F. The E-10 fuel increased emissions from the Achieva at both 20 (0.76 to 1.32 g/mi) and 0 °F (1.76 to 3.35 g/mi) but reduced emissions at -20 °F (3.55 to 2.85 g/mi). Total Hydrocarbons-IM240 Cycle. The hydrocarbon emissions (Figures 7-12) in general showed no trend as the test temperature decreased from 20 to -20 °F with base fuel in NM mode. When operating the Taurus on E-10 fuel the emissions increased from 0.19 to 0,35 g/mi but the emissions from the Achieva decreased from 1.44 to 0.60 g/mi as the test temperature decreased from 20 to -20 °F. Disconnecting the oxygen sensor on the Achieva caused the emissions to increase from 4.34 to 17.60 g/mi with base fuel and decrease from 5.31 to 1.54 g/mi with E-10 14 ------- fuel as test temperature decreased from 20 to -20 °F. Disconnecting the oxygen sensor on the Taurus caused the emissions to increase from 2.98 to 4,00 g/mi with base fuel and from 2,34 to 3.06 g/mi with the E-10 fuel (20 to -20 °F). Disconnecting the EGR on both vehicles generally did not substantially result in significant emission changes as the test temperatures decreased. The E-10 fuel did not produce consistent emission trends as the test temperatures decreased. Achieva emissions ranged from 0.13 g/mi at 20 °F (EGR mode with base fuel) to a high of 17.60 g/mi at - 20 °F (02 mode with base fuel) and the Taurus emissions ranged from 0.16 g/mi at both 20 and 0 °F (EGR mode with E-10 fuel) to a high of 4.00 g/mi at -20 °F (02 mode with base fuel) . Generally, in the 02 mode when both vehicles were at maximum emission levels the E-10 fuel reduced emissions. Carbon Monoxide-HDDS Cycle. Carbon monoxide emissions (Figures 13-18) increased as the test temperature decreased with the Taurus when tested with all modes and with both fuels. In the NM mode the emissions from the Taurus were 2.08 g/mi (75 °F, SG fuel) and 23.40 g/mi at - 20 °F with base fuel and 29.40 g/mi at the same temperature with E-10 fuel. The emissions from the Achieva generally increased as test temperatures decreased in all modes and with both fuels. In the NM mode the emissions from the Achieva were 4.61 g/mi (75 °F« SG fuel) and 25.65 g/mi at -20 °F with base fuel and 28.20 g/mi at 0 °F with the E-10 fuel. Again, testing in the mode in which the oxygen sensor was disconnected (allowing the vehicle to operate slightly rich), resulted in the greatest CO emissions. CO emissions ranged from a low of 3.12 g/mi, at 75 °F, for the Achieva (EGR disconnected), to a high of 154,34 g/mi at -20 °F (02 sensor disconnected), and for the Taurus a low of 2.08 g/mi, at 75 °F (NM mode), to a high of 163.54 g/mi at -20 °F (02 disconnected). The E-10 fuel lowered emissions from the Taurus at both 20 and 0 °F at all test modes but increased emissions at -20 °F at both NM and EGR test modes (23.40 to 29.40 g/mi and 21.72 to 26.34 g/mi, respectively). The E-10 fuel lowered emissions from the Achieva at -20 °F at all test modes and at 20 °F at the 02 and EGR test modes but emissions were increased at 20 DF (9.20 to 10.60 g/mi) NM test mode and at 0 °F in both the NM and 02 test modes (16.95 to 28.20 g/mi and 133.67 to 146.49 g/mi, respectively). Carbon Monoxide-IM240 Cycle. The carbon monoxide emissions (Figures 19-24) from the Achieva generally increased with base fuel and decreased with the E-10 fuel (all modes) as test temperatures decreased. Emissions from the Taurus generally increased with both fuels and all modes as test temperatures decreased. As expected disconnecting the oxygen sensor produced more CO emissions. The Achieva was generally the greater emitter. Emissions from the Achieva ranged from 2.04 g/mi (EGR mode, SG fuel at 75 °F) to a maximum of 186.35 g/mi (02 mode, base fuel at -20 DF) and from the Taurus ranged from 1.25 g/mi (EGR mode, SG fuel at 75 °F) to a maximum of 98.48 g/mi (02 mode, base fuel at -20 °F). The E-10 fuel produced a general reduction in CO emissions from both vehicles when compared to the base fuel CO emissions. Oxides of Nitrogen-UDDS. Figures 25-30 show vehicle emissions for both vehicles at all test conditions. The Achieva produced more NOx than the Taurus in the NM mode with all fuels and at all test temperatures. Disconnecting the EGR generally increased the NOx emissions from the Achieva and the Taurus as the test temperatures decreased. The Achieva's emissions ranged from a low of 0.15 g/mi at 75 °F (02 mode with base fuel) to a high of 2.02 g/mi at 75 °F (EGR 15 ------- mode). The Taurus's emissions ranged from a low 0.58 g/mi at 20 °F (NM mode) to a high of 1.09 g/mi at -20 °F (EGR mode). Oxides of Nitrogen-IM240. Figures 31-36 show vehicle IM240 data for both vehicles at all test conditions. In the NM mode the E-10 fuel generally increased NOx emissions (compared to base fuel emissions) from the Achieva but generally decreased the NOx emissions from the Taurus. At the lower (<75 °F) test temperatures the Taurus NOx emissions were generally greater with base fuel and the Achieva emissions were generally greater with the E-10 fuel. In general, the E-10 fuel generally increased NOx emissions from the Achieva and generally reduced emissions from the Taurus. Toxic Emissions Benzene. Besides being present in the fuel itself, benzene is emitted from the tailpipe as a result of its formation during the combustion process involving other fuel components, such as cyclohexane and the alkylaromatics.1,12 In one study from 2 to 7 % of the benzene was determined to be the result of the rearrangement of these molecules during combustion.13 Benzene emissions (Figures 37-42) increased as test temperature decreased with one exception the Achieva when tested with E-10 fuel at -20 °F, in the NM mode where the emissions decreased from 54.31 (0 °F) to 41.12 mg/mi (-20 °F). A regression plot of HC vs benzene had a R2 of 0.973 and a slope of 28.930 for the both vehicles, all test modes, all fuels, and all test temperatures. Benzene emissions from the Achieva ranged from a low of 8.03 mg/mi, at 75 °F (EGR mode), to a high of 510.02 mg/mi at 0 °F (02 mode and base fuel), and for the Taurus a low of 8.34 mg/mi, at 75 °F (EGR mode) to a high of 303.94 mg/mi at -20 °F (02 mode and base fuel). The E-10 fuel (NM mode) reduced benzene emissions, as compared to the base fuel, from the Taurus at 20, 0 and -20 °F (10.57 to 29.33 mg/mi, 72,51 to 67.71 mg/mi, and 116.79 mg/mi respectively) test temperatures. Achieva emissions increased at both 20 and 0 °F but decreased at -20 °F (14.89 to 45.44 mg/mi, 52.31 to 99.53 mg/mi, and 115.59 to 96.71 mg/mi respectively). 1,3-Butadiene. 1,3-Butadiene is not a gasoline component but a by-product of the combustion process. This compound was emitted primarily in the initial 2 minutes of vehicle start-up, when the air-to-fuel mixture was rich and the vehicle's emission control system was warming up. Figures 43-48 show the emission rates for both vehicles at all test conditions. In the NM mode 1,3-Butadiene emissions from the Taurus increased and from the Achieva generally increased as test temperature decreased for both fuels. A regression plot of HC vs 1,3-butadiene had a R2 of 0.875 and a slope of 5.023 for all vehicles, fuels, modes, and test temperatures. The E-10 fuel, in the NM mode, generally reduced emissions from the Taurus and generally increased those from the Achieva. The Achieva emissions ranged from a low of 1.10 mg/mi, at 75 °F, (EGR mode) to 16 ------- a high of 77.68 mg/mi, at 0 °F (02 mode with base fuel), and the Taurus emissions ranged from 1.11 mg/mi, at 75 °F (NM mode), to a high of 47.59 mg/mi, at -20 °F (02 mode with base fuel). The E-10 fuel, in the NM mode, reduced emissions from the Taurus at both 20 and 0 °F but increased emissions at -20 °F (6.51 to 4.58 mg/mi, 10.81 to 10.61 mg/mi, and 12.73 to 16.23 mg/mi, respectively). The E-10 fuel increased emissions from the Achieva at both 20 and 0 °F but decreased emissions at -20 °F (1.71 to 5.41 mg/mi, 5.40 to 10.11 mg/mi, and 13.64 to 9.93 mg/mi respectively). Formaldehyde and Acetaldehyde. Formaldehyde (Figures 49-54) and acetaldehyde (Figures 55- 60) were not present in the fuel but are by-products of the incomplete combustion of the fuel. These two aldehydes are usually the major aldehydes emitted, with formaldehyde the major emission product A regression plot of HC vs formaldehyde had a R2 of 0.472 and a slope of 2.091 for all vehicles, fuels test modes, and test temperatures indicating little correlation and further regressions varying vehicles, modes or temperatures showed no correlation improvement. Regressions (HC vs formaldehyde) with the fuels showed that with base fuel, all vehicles, modes, and test temperatures there was no improvement in the correlation but with the E-10 fuel the correlation increased with an R2 of 0.897 and a slope of 4.167, indicating good correlation HC vs formaldehyde with this fuel. The Achieva formaldehyde emissions ranged from a low of 2.47 mg/mi at 20 °F (NM mode with base fuel), to a high of 30.09 mg/mi at -20 °F (02 mode with base fuel) and the Taurus formaldehyde emissions ranged from 4.56 mg/mi at 20 °F (EGR mode with base fuel), to 36.09 mg/mi at -20 °F (02 mode with base fuel). The E-10 fuel (NM mode) generally increased formaldehyde emissions from both vehicles. A regression plot of HC vs acetaldehyde had a R2 of 0.218 and a slope of 5.897 for all vehicles, fuels, modes and test temperatures. Regression analysis of HC vs acetaldehyde data from the E-10 fuel showed an excellent correlation with an R2 of 0.931 and a slope of 23.275. The Achieva emissions ranged from 1.45 mg/mi at 75 °F (EGR mode with SG fuel) to a maximum of 33.84 mg/mi at -20 °F (02 mode with base fuel) and the Taurus ranged from 0.86 mg/mi at 75 CF (NM mode with SG fuel) to a maximum of 28.37 mg/mi at -20 °F (02 mode with base fuel). The E-10 fuel (NM mode) increased acetaldehyde emissions from both vehicles with the increase ranging 1,98 to 10.41 mg/mi at 20 °F to a maximum increase of 2.35 to 31.04 mg/mi at 0 °F from the Achieva and the Taurus emissions ranging from 2.86 to 9.95 mg/mi at 20 °F to a maximum of 4.30 to 25.21 mg/mi at -20 °F. The acetaldehyde emissions were greatest when the vehicles were operated in the 02 mode. Total aldehyde emissions were also greatest when the vehicles were operated in the 02 mode (vehicle running rich). Particulate Emissions PM2.5 and PM10 - UDDS Cycle. The particulate emissions (PM2.5 and PM10) from both vehicles followed the HC and CO trend, and increased as the test temperatures decreased. The PM2.5 particles emissions were about the same as the PM10 particle emissions (Figure 61) indicating that gasoline fueled particulate are less than 2.5 um. Figure 62 is a regression plot of THC vs PM2.5 for both vehicles at all test conditions, showing no correlation at these conditions. A regression analysis of the Taurus emissions showed some correlation at all test conditions (R2 17 ------- of 0.494) and good correlation when the data was tested with and without the 02 mode in the 02 mode (R2 of 0.833 and 0.932 respectively). The Achieva show little THC vs PM2.5 correlation as regression analysis was performed at different test modes and fuels. Individual cycle particle (PNG.5) emissions ranged from a low of 1.30 mg/'mi for the Achieva tested at 75 °F in the EGR mode on SG to a high of 121.15 mg/mi at -20 °F in the 02 mode on base fuel. The PM2.5 emissions from the Taurus ranged from a low of 0.70 mg/mi at 75 °F in the NM mode on SG fuel to a high of 194.50 mg/mi at -20 °F in the 02 mode on base fuel. Particulate emissions from the Achieva were generally increased in the NM and EGR modes but decreased in the 02 mode when tested with the E-10 fuel. Particulate emissions from the Taurus were decreased when tested in the NM and 02 modes and generally decreased in the EGR mode when tested on E-10 fuel. Taurus PM2.5 emissions (excluding 75 °F tests) were from about 1.5 to almost 5 times, depending on temperature and mode, that of the Achieva. The vehicles produced the most PM2.5 emissions when tested in the 02 mode and operating on base fuel. The E-10 fuel generally reduced particle emissions from the Taurus (all modes) but the Achieva emissions were not as well defined. PM2.5 and PM10 - IM240 Cycle. The particle emissions from the IM240 cycle (excluding SG fuel) ranged from a low of 1.65 mg/mi for the Achieva tested at -20 °F in the 02 mode with E- 10 fuel, to a high of 85.00 mg/mi from the same vehicle tested at -20 °F in the 02 mode using the base fuel. The particle emissions, in general, increased as the test temperature decreased with the most particle emissions generally at -20 °F. The Taurus generally had a higher emission rate than the Achieva and the E-l 0 fuel did not show any overall emission trends. Alcohols In addition to the HCs and aldehydes, the three alcohols, methanol (MeOH), ethanol (EtOH), and 2-propanol are determined from each vehicle test. These compounds are not present in the base fuel but are combustion products. Regression analysis of THC vs EtOH and THC vs MeOH, from both vehicles data, showing the influence of test fuel on the emissions are shown in Figures 63-66. Ethanol was added to the base fuel, to prepare the E-10 fuel, and the base fuel did not contain either methanol or 2-propanol. No regression plots were prepared for the 2-propanol emissions. Since, the combined vehicles test data did not show any THC vs EtOH correlation each of the vehicles were then individually regressed. Achieva regression analysis for THC vs EtOH with base fuel (all modes and test temperatures) shows no correlation (R2 of <0.10 but some correlation was present with the E-10 fuel (R2 of 0.773). Achieva EtOH emissions ranged from <0.01 mg/mi (low value at several conditions) to a high of 123.92 mg/mi at 0 °F with E-l 0 fuel in 02 mode. Taurus regression analysis for THC vs EtOH with base fuel (all modes and test temperatures) shows no correlation with either fuel (R2 of <0.10 with base and R2 of 0.167 with E-10). Taurus EtOH emissions ranged <0.01 mg/mi (low value at several conditions) to a high of 113.74 mg/mi at -20 °F with E-10 fuel in 02 mode. Achieva regression analysis for THC vs MeOH with base fuel had a fair correlation (R2 of 0.697) and a good correlation with E-10 fuel (R2 of 0.853). Achieva emissions ranged from 0.53 mg/mi at 20 °F with base fuel in the EGR mode to 275.60 mg/mi at 0 °F with the E-10 fuel in 02 mode. Taurus regression analysis for 18 ------- THC vs MeOH with base and E-10 fuels showed good correlations (R2 of 0.814 and 0.816 respectively), Taurus emissions ranged from 0.01 mg/mi at 75 °F with base fuel in NM mode to 138.84 mg/mi at -20 °F with E-10 fuel in 02 mode. Achieva regression analysis of THC vs 2- propanol with base fuel showed a good correlation with both base and E10 fuels (R2 of 0.887 and 0.839 respectively). Achieva emissions ranged from <0.01 mg/mi (at several conditions) to 7.62 mg/mi at 0 °F with base fuel in the 02 mode. Taurus regression analysis for THC vs 2-propanol with both base and E-10 fuels were fair (R2 of 0.576 and 0.706 respectively). Taurus emissions ranged from 0.01 mg/mi (at several conditions) to 4.41 mg/mi at 0 °F with base fuel in 02 mode. SUMMARY AND CONCLUSIONS In reviewing the regulated emissions (HC, CO, and NOx), the toxic emissions (benzene, 1,3-butadiene, formaldehyde, and acetaldehyde). and the particulate emissions (PM2.5 and PM10) data it should be noted that these are emissions from only two vehicles. These test vehicles could or could not be representative of the on-road fleet. The malfunction conditions that were introduced are extreme conditions in which the vehicle's oxygen sensor and the EGR valve were rendered completely inoperable. In actuality, the condition of these simulated malfunctions (oxygen sensor and EGR valve disconnected) on on-road vehicles could be anywhere in the range of being completely operable to inoperable. Limited resources restricted our testing to two vehicles and to duplicate runs (one at 75 °F) at 20, 0 and -20 °F. Also, due to resource limitations we were able to take only single PM2.5 and PM10 particulate filter from each of the UDDS test cycles (all three phases combined) rather than individual PM2.5 and PM10 particle filter from each of the UDDS's three phases. Hydrocarbons-UDDS cycle - Hydrocarbons generally increased as test temperature decreased and the most HCs were emitted when the 02 sensor was disconnected. The E-10 fuel reduced emissions from the Taurus and generally from the Achieva. The Taurus produced the maximum emissions (10.42 g/mi) at -20 °F with the 02 sensor disconnected. The Achieva produced the maximum emissions (12.31 g/mi) at -20 °F with the 02 sensor disconnected. The Achieva was in general the greater emitter. Hydrocarbons-1M240 cycle - In general, lowering the test temperature and disconnecting the 02 sensor increased the HC emissions. The E-10 fuel generally reduced the HC emissions. The vehicles produced the maximum emissions, Achieva 17.60 g/mi and Taurus 4.00 g/mi, at -20 °F (base fuel) when the 02 sensor was disconnected and both vehicles produced minimum emissions 75 °F when tested on the SG fuel. Carbon Monoxide-UDDS cycle - There was a general increase in CO emissions as the test temperature decreased and disabling the 02 sensor resulted in the most CO emissions. The E-10 fuel generally reduced CO emissions from both vehicles. Both vehicles produced the most emissions when the 02 sensor was disconnected 19 ------- Carbon Monoxide-IM240 cycle - There was a general increase in CO emissions as the test temperature decreased and the most CO was emitted when the 02 sensor was disconnected. The E-10 fuel generally reduced CO emissions from both vehicles. Oxides of Nitrogen-UDDS cycle - Disconnecting the EGR generally produced greater NOx emissions from both vehicles as test temperatures decreased. The Achieva was generally the greater emitter. Oxides of Nitrogen-IM240 cycle - The Achieva produced the greatest emissions when tested in the EGR malfunction mode but the Taurus did not indicate any mode sensitivity. In general, the E-10 fuel increased emissions from the Achieva and reduced emissions from the Taurus. Benzene - Benzene emissions generally increased as test temperature decreased. Disconnecting the 02 sensor produced the highest benzene emission rate. The E-10 fuel generally reduced benzene emissions from the Taurus but generally increased emissions from the Achieva. Regression analysis shows good correlation between HCs and benzene with both vehicles at all test conditions. 1,3-Butadiene - The 1,3-butadiene emissions generally increased, from both vehicles, as the test temperature decreased. Disconnecting the 02 sensor resulted in greater emissions. The E-10 fuel generally reduced emissions rates from both vehicles. Regression analysis of HCs and 1,3-butadiene indicated a good correlation (R2 0.875) for the all test data. Aldehydes - Formaldehyde and acetaldehyde emissions from both vehicles generally increased as the test temperatures decreased when testing with the base and the E-10 fuels. Regression analysis of HCs and formaldehyde showed slight correlation (R2 0.472 for both vehicles) and a regression of HCs and acetaldehyde showed no correlation (R3 0.218 for both vehicles) PM2.5 and PM10 particulate-UDDS cycle - The PM2.5 and PM10 particulate emissions levels were comparable (indicating that all PM emissions are less than 2.5 um). Emissions from both vehicles followed the HC trend and increased as the test temperatures decreased. The E-10 fuel generally reduced particulate emissions from the Taurus but the Achieva showed no trends. Disconnecting the 02 sensor on the vehicles generally produced the most emissions. Taurus particulate emissions were from 1.5 to about 5 times those of the Achieva. PM2.5 and PM10 partieulate-IM240 cycle - Particulate emissions generally increased as test temperature decreased. In general, disconnecting the 02 sensor produced the most emissions. The E-10 fuel produced a general reduction in emissios from the Achieva but a general increase in emissions from the Taurus. 20 ------- Alcohols-THC vs EtOH emissions showed some correlation with them E-1Q fuel but the Taurus showed no correlation with either fuel. Both vehicles showed THC vs MeOH correlation with both base and E-10 fuels. Regression analysis of THC vs 2-propanol individual vehicle data sets showed good correlation for the Achieva and fair correlation for the Taurus. 21 ------- ACKNOWLEDGMENTS The authors acknowledge and express gratitude to William Crews and Richard Snow of Clean Air Vehicle Technology Center, Inc. for providing analytical assistance. We also acknowledge Jerry Faircloth, Versal Mason, and Phil Carter of ManTech Environmental for vehicle testing and data processing assistance. The authors would also like to express their appreciation to Jim Braddock of EPA for his technical and editorial assistance in preparing this manuscript 22 ------- DISCLAMER The information in this document has been funded wholly by the United States Environmental Protection Agency under Contract 68-D5-0156 to Clean Air Vehicle Technology Center, Inc. It has been subjected to the Agency's peer and administrative review and has been approve for publication as an EPA document. Mention of trade names or commercial products does not constitute an endorsement or recommendation for use. 23 ------- REFERENCES 1. Health Effects Institute Communications, Research Priorities for Mobile Air Toxics, No. 2 (1993) 2. D. W. Dockery, C. A. Pope., Ill, Annu. Rev. Public Health 1997, 15,107-132. 3. Particulate air pollution and daily mortality: Replication and validation of selected studies; Health Effects Institute: Boston, 1995 4. S. Cadle, P. A. Mulawa, J. Ball, C. Donase, A. Weibel, J. C. Sagebeil, K. T. Knapp, R. Snow, Environ. Sci Technol. 1997, 31,3405-3412 5. R. Snow, L. Baker, W. Crews, C. O. Davis, J. Duncan, N. Perry, P. Siudak, F. Stump, W. Ray, J. Braddock, "Characterization of emissions from a methanol fueled vehicle". J. Air Pollu. Control Assoc. 39:48(1989) 6. F. Stump, S. Tejada, F. Black, W. Ray, W. Crews, R. Davis, "Compound injection to assure the performance of motor vehicle emissions sampling systems". SAE Paper 961118, Society of Automotive Engineers, Warrendale, PA, 1996 7. Code of Federal Regulations, Title 40, Part 86, U. S. Government Printing Office, Washington, DC, 1983 8. F. Stump, K. Knapp, and W. Ray, "Seasonal Impact of Blending Oxygenated Organics with Gasoline on Motor Vehicle Tailpipe and Evaporative Emissions," J. Air Waste Manag. Assoc. 40,872-880,(1990). 9. S. Tejada, J. Sigsby, "Identification of chromatographic peaks using Lotus 1-2-3", J. Chromatogr. Sci., 26: 292 (1988) 10. S. Tejada, "Evaluation of silica gel cartridges in situ with acidified 2,4- Dinitrophenylhydrazine for sampling aldehydes and ketones in air", Anal Chem. 26:167(1986) 11. E. W. Kaiser, W. O. Siegl, D. F. Cotton, R. W. Anderson, "Effects of fuel structure on emissions from a spark-ignited engine II. Naphthalene and aromatic fuels", Environ. Sei. Technol, 26,1581-1586 (1992) 12. E, W. Kaiser, W. O. Siegl, Y. I. Henig, R. W. Anderson, F. H. Trinker, "Effects of fuel structure on emissions from a spark-ignited engine", Environ. Sci. Technol., 25, 2005 (1991) 13. F. D. Stump. K. T. Knapp, W. D. Ray, C. Burton, R. Snow, "The seasonal impact of blending oxygenated organics with gasoline in motor vehicle tailpipe and evaporative emissions-Part II", SAE Paper 902129, Society of Automotive Engineers, Warrendale, PA, 1990 24 ------- Figure 1. Achieva, THC, UDDS Cycle, NM mode Figure 2, Achieve, THC, UDDS Cycle, Q2 mode 2.5 -» •2D Ae-io Figure 3. Achieva, THC. UDDS Cycle, EGR mode 3 15 A 2 I 1.5 ca 1 0.5 it ~ A i-io ' V i 40 •20 0 20 40 60 80 Test Temperature, F Figure 4, Taurus, THC, UDDS Cycle, NM mode Test Temperature, F Figure 5. Taurus, THC, UDDS Cycle, 02 mode Figure 6, Taurus, THC, UDDS Cycle, EGR made tBase E-10 40 .20 0 20 40 CO 80 Test Temperature, F Test Temperature, F 25 ------- Figure 7. Achieves, THC, 1M240Cycle. NM mode 2.5 1.5 Base E-10 -4fl -20 0 20 40 10 Test Temperature, F Figure 8, Achieva, THC, IM24Q Cycle, Q2 mode 20 .?• 10 •40 -20 0 2d 40 Test Temperature, F tBase E-10 Fjgure 9. Achieva, THC, IM240 Cycle, EGR mode 0 20 45 60 so Test Temperature, F Figure 10, Taurus, THC, IM240 Cycle, NM mode / 6as« $W Test Tgnperature, F Figure 11, Taurus, THC, IM240Cycle, 02 mode Figure 12. Taurus, THC, IM24Q Cycle, ESR mode t Base E-10 -40 -20 0 20 40 SO Test Temperature, F 0.25 0.2 tBase E-10 40 -20 0 20 « 60 BO Tast Temperature, F 26 ------- Figure 13. Achieva, CO, ODDS Cycle, NM mode f 15 Base E-10 40 -20 0 20 40 60 Test Temperature, F Figure 14. Achieva, CO, UDDS Cycle, Q2 mode 200 150 € wo so ^ * 1 A A i -40 -20 g 20 40 Test Temperature,? tBas? E-10 Figure 15, Achieva, CO, UDDS Cycle, EGR mode 25 20 15 -40 -20 i 0 20 40 Test Tsmperaturs, F Base E-10 60 80 Figure 16, Taurus, CO, UDDS Cycle, NM mode -#¦ 0 20 40 Test Temperature, F tSase E-10 <0 $0 Figure 1 7. Taurus, CO, UDDS Cycle, 02 mode Figure 18. Taurus, CO, UDDS Cycte, EGR mode 200 150 100 0 A A O i A Obm« A E-10 40 -20 0 20 40 B0 10 Test Temperature, F ¦4- * tBase E-10 -40 -20 0 20 40 TeslTanperature, F 27 ------- Figure 19. Achieva. CO, 1M240 Cycle, NM mode Figure 20, Achieva, CO, IM24Q Cycle, 02 mode Test Temperature, F Test Temperature, F Figure 21, Achieva, CO, 1M24Q Cycle, EGR mode 5.5 s 4.5 4 1 3.5 05 3 2J 2 1J -40 IT 0 20 Test Temperature, F 40 'Bait LE-10 Figure 22. Taurus, CO, IM240 Cycle, NM mode 1 ''Base LE-10 40 -20 0 2D 4C SO Test Tsnperature.F Figure 23. Taurus, CO. IM240 Cycle, 02 mode Figure 24. Taurus, CO, IM240 Cycle, EGR mode ¦i &o Test Temperature, F A O ir /Base E-10 -40 -20 0 20 40 60 Test Tenpasture, F 28 ------- Figure 25. Achleva, NOx, UDDS Cycle, NM modi Test Temperature, F Figure 26, Achleva, NOx, UDDS Cycle, Q2 mode 1.2 ,0.6 0.4 0.2 -0- tBase E-10 40 -2(1 0 20 40 60 89 Tesi Tanperatura, F Figure 27. Achieva, NOx, UDDS Cycle, EGR mode 2.1 2 1.9 1.8 -•1.7 = "1.6 1.5 1.4 13 1.2 -40 A <> Jt 4- 0 20 40 TestTernperature, F i Base E-10 80 Figure 28. Taurus, NOx, UDDS Cycle NM mode 0.9 0.8 0,7 ra °'6 0.8 0.4 0.3 -M -20 t Base 6.10 0 20 40 Test Temperature, F « 10 Figure 29. Taurus, NOx, UDDS Cycle, Q2 mode Figure 30, Taurus, NOx, UDDS Cycle EGR mode 1.1 0.9 a,t 0.7 0.6 -U -20 let Temperature, F E-1fl 20 40 m Test Temperature, F 29 ------- Figure 31, Achieva NQx, IM240 Cycle, NM mode 0.9 0.S5 0,75 0.7 0.65 1 Base E'10 0 20 40 6D Test Temperature, F Figure 32, Achleva, NQx, 1M240 Cycle, Q2 mode f 3 ¦l,.,,,,.#, 1 -40 -20 tBase E-10 0 2D 40 Test Temperature, f Figure 33. Achleva, NQx, tM240 Cycle, EGR mode 4 2.5 i Base 1-10 0 20 40 60 Test Temperature, F Figure 34, Taurus, NQx, 1M24Q Cyel% NM made 1.3 1.2 1.1 1 0.9 0J 0.7 0.6 * Base ki-10 4Q -20 8 20 40 60 Test Temperature, F Figure 35. Taurus, NOx, IM240 Cycle 02 mode Figure 36. Taurus, NOx, IM240 Cycle, EGR mode Test Temperature, F Test Temperalure, F 30 ------- Figure 37, Achleva, Benzene, UDDS Cycle, NM mode 41 -20 0 20 40 Test Temperature, F Figure 38. Achleva, Benzene, UDDS Cycle, 02 mode 'B»S9 e-u Test Temperature, F Figure 39, Achieva. Benzene, UDDS Cycle. EG"? made Figure 40, Taurus, Benzene, UDDS Cycle NM mode d 20 40 60 Test Temperature, F Test Temperature, F Figure 41, Taurus, Benzene, UDDS Cycle 02 mode Figure 42. Taurus, Benzene, UDDS Cycle EGR mode ' Base LE-10 200 Test Temperature, F 0 20 40 SO 80 TestTgrppersture, F 31 ------- Figure 43, Achieva, 1,3-Butadiene, UDPS Cycle, NM mode 10 0 1 - " m 6 A 0 ± t Base E-10 40 *20 0 20 40 Test Temperature, F 80 Figure 44. Achieva, 1,3-Butadlene, UDDS Cycle, Q2 mode Tat Temperature. F Figure 45. Achieva, 1,3-Butadiene, UDDS Cycle, ESR mode Figure 46. Taurus, 1,3-Butadiene, UDDS Cycle NM mode Tei Tanperature, F Test Temperalure, F Figure 47, Taurus, 1,3-Butadiene, UDDS Cycle 02 mode Figure 48. Taurus, 1,3-Butadiene, UDDS Cycle, EGR mode > 30 &Bas Ae-k 40-20 0 20 40 60 80 Test Temperature, F tBase E-10 40 -20 0 20 44 60 Tast Temper aim F 32 ------- Figure 49, Achieva, Formaldehyde, UDDS Cycle, NM mode Figure 50, Achieva, Formaldehyde, UDDS Cycle, Q2 mode Base i-10 4(9 >20 0 20 40 . 60 TesITonperalure, F Bail MO 40-20 8 20 40 60 80 TestTempefatuie, F Figure 51. Achieva, Formaldehyde, UDDS Cycle, EGR mode Figure 52. Taurus, Formaldehyde UDDS Cycle, NM mode Test Temperature, F Test Temperature, Figure 53, Taurus, Formaldehyde. UDDS Cycle, 02 mode Figure 54. Taurus, Formaldehyde UDDS Cycle, EGR mode 40 3S ¦ 30 ^ 25 . 20 15 to 5 0 Bast E-10 0 20 40 Test Temperature. F 80 ia t" 0 20 40 Test Temperature, F Osase A E-10 33 ------- Figure 55, Achieva, Acetaldehyde, LIDDS Cycle, MM mode Test Temperature, F Figure 56. Achieva, Acetaldehyde, UDDS Cycle, Q2 mode 300 -M -20 ^ 0 i Bast E-10 20 40 60 TetTamperatufe, F Figure 57, Achieva, Acetaldehyde, UDDS Cycle, EGR mode Figure 58, Taurus, Acetaldehyde, UDDS Cycle NM mode 'Base kE-10 /Base Test Temperature, F 0 20 40 60 Test Temperature, F Figure 59. Taurus, Acetaldehyde, UDDS Cycle, 02 mode Figure 60. Taurus, Acetaldehyde, UDDS Cycle EGR mode 140 120 too so to : 40 20 0 -20 0 20 A Test Temperature, F t Base E-10 20 -40 -20 0 20 40 TeeiTamperalure, F 1 Base E-10 60 34 ------- Figure 61, PM2.5 vs Pml 0, Both vehicles of all test conditions Figure 62, THC vs PM2.5, Both vehicles err oil test conditions 210 R* 2=0 9M Sope=l .009 CowtanNQ.32; tf I c 100 20 40 60 160 R A 2=0.275 Scpe-6.683 C< 170 I HQ I 80 - ,J&"o 0 2 8 10 12 14 6 36 18 Figure 63. THC vs EtOH, Both vehicles, base fuel all conditions Figure 64-. THC vs EfOH, Bo-h vehicles, E-l 0 fuel all conditions ~.04! Constcrt-0.486 r< ~ 2-C.505 SbDS-10.14? Ccrstent-5 642 S20 - 80 ¦ Figure 65. THC vs MeOH, Both vehicles, base fuel ail conditions Figure 66, THC vs MeOH, Both vehicles, E-l0 fuel ail conditions R ~ 2=0-558 UOOG* 1-768 COftS?arsJ=3.Q46 ft-- 2-G.92 1 aope-25.656 Conston*- -32.S78 •0 2 4 4 S ] 0 12 14 16 18 0 2 4 6 8 10 12 35 ------- 9 10 11 12 13 14 IS 16 17 18 19 20 21 iOl 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 4* 44 45 46 47 48 49 SO 51 52 53 54 55 56 57 50 59 60 61 ~ 01 €2 S3 64 >01 £5 66 101 67 68 63 70 71 72 iOl 73 74 75 ?S iOl 77 78 79 80 81 82 83 84 85 86 87 83 89 90 Detailed Hydrocarbon Table Compound METHANE ETHYLENE ETHANE ACETYLENE PROPANE PROPYLENE PROPADIENE KETKYIACETYLENE IS0-BTJTANE *** UNKNOWN *** 1-BUTENE ISO-BUTYLENE 1,3-BUTADIENE N-BUTANE 2, 2-DIMETHYLPRCiPANE TRAMS - 2-BUTENE l-BUTEN-l-YNE 1-BUTYNE CIS-2 -BUTENE »*« UNKNOWN »** 1.3-BUTAD1YNE 1.2-BUTADIENE 3-METHYL-1-BUTENE ISO-PENTANE 1.4-PENTADIBNE 2-BUTYNE 1-PENTENE 2-METHYL,-1,3- BUTADIENE 2-METHYL-1-BITTEN-3-YNE 2-METHYL-1 -BUTENE N-PENTANE ISQPRENE TRANS-2-PENTENE 3.3-DIMETHYL-1-BUTENE CLS-2-PENTENE 2-KETHYL-2-BUTENE CI S -1, 3 - PENTAD IENE CYCLOPENTADIENE 2, 2-DIMETHYLBUTANE TRANS -1,3- PENTADIENE CSHB C5HE CYCLOPENTENE C5H8 4-METHYL-1-PENTENE 3-HETHYL-1-PENTENE CYCLOPENTANE "* UNKNOWN *** 2,3-DIMETHYLBUTANE 4-HETHYL-CIS - 2 -PENTENE 2.3-DIMETHYL-1-BUTENE 2-hethylfentane 4 -METHYL-TRANS - 2 - PENTENE C5H6 C5H8 *** UNKNOWN *** *** UNKNOWN *** »** UNKNOWN *** 3-METKYLPENTANE 2-METHYL-I-PENTENE 1-HEXENE C6H1Q C6H10 2-ETHYL-1-BUTENE N-HEXANE CIS-3-HEXENE TRANS -3-HEXENE TRANS -2-HEXENE 2-METHYL-2 -PENTENE 3-METHYLCYCLOFENTENE CIS - 3-METHYL-2-PENTENE 4-METHYLCYCLQPENTENE CIS-2-HEXENE C6H1G UNKNOWN TRANS - 3-METHYL-2-PENTENE 2,2 -DIMETHYLPENTANE METHYLCYCLOPENTANE *•** UNKNOWN *** *•** UNKNOWN **» 2.4-DIMETHYLPENTANE 2.3-DIMETHYL-2 -BUTENE 2,2,3-TRIMETHYLBUTANE C6H8 DIMETHYLCYCLOPENTENE 2.4-DIMETHYL-1-PENTENE 1-METHYLCYCLOFENTENE BENSENE 4,4-DIMETHYL-2-PENTENE 3, 3-DIMETHYLPENTANE TRANS -2-METHYL-3-HEXENE CYCLOHEXANE C7H14 C7H14 4-METHYL-1-HEXENE C7H12 91 TRANS-4 -METHYL-2-HEXENE 92 2-METHYLKEXANE 93 2,3-DIMETHYLPENTANE 94 *** UNKNOWN *** 95 1,1-EIMETHYLCYCLOPENTANE 96 3-METHYLHEXANE 96501 CYCLOHEXENE 97 TRANS-S-METHYL- 2-HEXENE 98 CIS-1,3-DIMSTHYLCYCLOPENTANE 99 TRANS-1,3-DIMETHYLCYCLOPENTANE 100 TRANS-1,2-DIMETHYLCYCLOPENTANE 101 3,4-DIMETHYL-TRANS -2-PENTENE 102 ISO-OCTANE 103 3-METHYL-TRANS 3-HEXENE 104 TRANS-3-HEPTEKE 105 N-HEPTANE 105501 1,3 -DIMETHYLCYCLOPENTENE 105502 1,4-DIMETHYLCYCLOPENTENE 106 CIS-3-METHYL-3-HEXENE 107 2-METHYL-2-HEXENE 108 TRANS-2-HEPTEKE 109 3-ETHYL-2-PENTENE 109501 C7H12 110 2-METHYL-2-HEXENE 111 1,5-DIMETHYLCYCLOPENTENE 111500 C3S-2-HEPTENE 111501 2,3-DIMETHYL- 2 -PENTENE 111502 3-ETHYL CYCLOPENTENE 112 4-ETHYL CYCLOPENTENE 112500 Z,2-DIMETHYLHEXANE 112501 1-CIS-2-DIMETHYLCYCLOPENTANE 113 METYHLCYCLOHEXANE 114 1,1,3 -TRIMETHYLCYCLOPENTANE 115 CSH14 116 C8H14 117 *** UNKNOWN *** 118 2,5-DIMETHYLHEXANE 119 2,4-DIMETHYLHEXANE 119501 2,2,3-TRIMETHYLFENTAN3 119502 3-METHYLCYCLOKEXSNE 119503 4-METHYLCYCLQKEXHNE 119504 C7H12 120 1,2,4-TRIMETHYLCYCL3PENTANE 120501 3,3-DIMETHYLHEXANE 121 C8H16 122 CSH14 123 C,T,C-1, 2, 3-TRIMETHYLCYCLOPENTANE 124 2,3,4-TRIMETHYLPENTAN2 124501 C7H12 124502 C8H16 125 1-ETHYLCYCLOPENTEN1 1255 01 C8H16 125502 2,3,3-TRIMETHYLPHNTANE 12€ TOLUENE 127 2,3-DIMETHYLHEXANE 127501 C8H14 1275 02 1,2,3-TRIMETHYLCYCLOPENTANE 123 2-METHYLHEPTANE 129 4-METHYLHEFTANE 129501 C7H12 130 3,i-DIMETHYLHEXANE 131 3-METKYLHEPTANE 131501 3-1THYLHEXANE 131502 C7H12 132 . 1,2,4-TRIMETHYLCYCLOPENTANE 132501 C8H1€ 133 TRANS-1,4-DIMETHYLCYCLOKEXANE 134 1,3-DIMETHYLCYCLOHEXANE 135 2,2,5-TRIMETHYLHSXANE 135501 TRIMETHYLCYCLOPENTANE 136 1-OCTENE 1365 01 TRANS-1-ETHYL - 3-METHYLCYCLQPENTAN 137 CIS -1-ETHYL - 3 ~ METHYLCYCLOPEfTTANE 138 C8H16 138501 CSH14 139 C8H16 140 C8H16 140501 C8H16 141 N-OCTANE 141501 C8H14 142 C8H16 142501 1,2-DIMETHYLCYCLOHEXANE 143 1,1,2-TRIMETHYLCYCLOPENTANE 143501 1,2,3-TRIMETHYLCYCLOPENTANE 143502 CSH14 144 CSH16 145 2-OCTENE 145501 C8H14 145502 C9H16 146 ISOPROPYLCYCLOPENTANE 147 *** UNKNOWN *** 148 2,3,5-TKIMETKYLHEXANE 149 C8H14 150 *** UNKNOWN *** 151 *** UNKNOWN *** 152 *** UNKNOWN *** 153 *** UNKNOWN *•* 154 *•* UNKNOWN 155 UNKNOWN 156 »•' UNKNOWN *»» IS? »~* UNKNOWN *** 158 »*» UNKNOWN *** 159 *** UNKNOWN *** 160 2,4-DIMETHYLHEPTANE 161 C8H14 161501 C8H14 1*2 2,6-DIMETHYLHEPTANE 162501 CSH18 162502 CSH18 163 n-PROPYLCYCLOPENTANE 164 *** UNKNOWN 165 2,5-DIMETHYLHEPTANE 165501 3,5-DIMETHYLHEPTANE 165502 C9H18 165503 3,3-DIMETHYLHEPTANE 166 1,1,4 -TRIMETHYLCYCLOHEXANE 166501 C9H1S 16? C9H1S 167500 C9H18 167501 C9H18 167502 C3H16 167503 C3H18 168 ETHYLBENSENE 169 2,3-DIMETHYLHEPTANE 169501 1,3,5-TRIMETHYLCYCLOKEXANE 170 3,4-DIMETHYLHEPTANE 171 MScP-XYLENE 172 •'* TOKITOWN 173 C9H18 173501 C9H18 174 3-METKYLOCTANE 174501 C8H14 175 C9H18 176 C9H18 176501 C9H18 177 C10H22 177501 STYRENE 178 1-NONENE 178501 2-NONENE 179 O-XYLENE 179501 CIS- 3-NGNENE 180 4-NONENE 181 *'• UNKNOWN »" 182 C9H16 182S01 C9H18 132502 C9H18 183 C9H18 184 C9H18 ? 185 C9H18 ? 186 C9H18 ? 187 N-NONANE 187501 C9H18 188 C9H18 189 C9H18 190 C9H18 191 C9H18 191501 C9H18 ? 192 C9H18 193 C9H18 193501 C9B18 ? 194 C9H18 195 IS OPRO PYLB 3N2 ENS 196 C10H22 ? 19? C10H22 1 197501 C10H22 ? 198 n-BUTYLCYCLOPENTANE 198501 C9H16 199 C10H22 ? 200 C10H22 201 C9H18 202 C10H22 ? 202501 *** UNKNOWN *** 203 C10H20 204 R-PROPYLBENZENE 205 C10H2 0 206 1-METHYL-3 -ETHYLBENZ2NE 207 1-METHYL-4 -ETHYLBENZENE 207501 C10H22 208 C10H22 205 1,3,5-TKIM2THYLBENZENE 210 C10H22 211 C10H20 212 C1CH22 212501 C1CH20 213 1-METHYL-2 -ETHYLBENZENE 214 C10H20 215 C10H20 216 C1OH20 21? o-METHYLSTYRENE 216 1,2,4-TRIMETKYLBENZENE 218501 m-METHYLSTYRENE 219 N-DECAN2 219500 C10H20 219501 C10H20 220 2-METHYLPROPYLBEE3ENE 221 1 - METHYLPROP YLB EN SENE 36 ------- *» 222 C11H24 295 C11H16 222501 1-METHYL-3 -ISOPROPYLBBNZEKB 300 C12K16 222502 C11H24 301 n-TRIDECANE 222503 p-METHYLSTYRENS 302 C12H16 223 1,2,3-TRIHETHYLBEN2EN2 303 C12H16 224 C11H24 3 04 2 -METHYLNAPHTHALRNE 224501 C1QHS0 305 *•* UNKNOWN *«* 224502 C11H24 3 06 *•» UNKNOWN *** 225 2 r 3 - DIHYDRCINDENE {INDAN) . 307 '«• UNKNOWN *** 22SS01 CIOKI2 308 1 - METHYLNAPHTHALENE 2 26 C10H20 330 KTBE 226501 INDENE 331 ETBE 227 1,3-DIETHYLBENZENE 332 TAME 22a *** UNKNOWN *** 333 UNKNOWN ***¦ 225 l-METHYL-3-n-PRC?YLBENZENE 334 -** UNKNOWN • #* 229501 1-METHYL-4-n-PRCFYLB ENZENE 335 -*** UNKNOWN 230 1,2-DIETKYLBEN2ENE 336 »*• UNKNOWN *«* 230501 n-BOTYLBENZEME 337 »*» UNKNOWN »«* 230502 C11K24 338 *»* UNKNOWN «** 231 C11K24 339 UN KNOW *»* 231501 1,4-BIETHYLBENZENE 340 METHANOL 232 C11H24 341 ETHANOL 232501 1,3-DIMETHYL-5-ETHYLBENZENE 342 K-PRO PANOL 233 1-METHYL-2-n-PROPYLBENZENE 343 2-PROPANOL 233501 C11H24 344 N-BUTANOL 234 1,4-DIMETHYL-2•ETHYLEENZENS 345 5EC-BUTANQL 235 1,3-DIMETHYL-4-ETHYLBENZENE 346. TBA 236 1,2-DIMETHYL-4-ETHYLBENZENE 347 *** UNKNOWN *** 236501 O-ETHYLSTYRENE 34a *** UNKNOWN 23*7 1,3-DIMETHYL-2-KTHYLBSNZENE 349 *~* UNKNOWN ** * 237501 m-ETHYLSTYRENE 350 ~»* UNKNOWN * * * 237502 C11K22 351 *** UNKNOWN • ** 233 C10K12 352 *»• UNKNOWN • * * 239 1,2-DIMETHYL-3-ETHYLBENZENE 353 *** UNKNOWN * * » 239501 C10H12 354 *** UNKNOWN **# 240 n-UNDECANE 355 *** UNKNOWN *** 240501 C10H12 356 *** UNKNOWN *** 241 l-HETKYL-4-{2-M2TKYLPR0PYL)BENZENE 357 *** UNKNOWN 44 * 241501 C11H14 353 *** UNKNOWN 4 4 * 242 1,2-DIMETHYL-3-ETHYLBEKZENE 359 •** UNKNOWN • #4 243 C11K14 360 *** UNKNOWN #*• 243501 C12H26 244 *** UNKNOWN *** 24S 1,2,4,S-TETRAMETKYLBENZENE 245501 C11H16 246 1,2,3,5-TETRAKETHYLBENZENE 247 C12H26 248 C11H14 249 C11H16 250 C11H16 251 C11H16 252 . ciiKie 252501 C11H14 253 •** UNKNOWN *** 254 »** UNKNOWN *** 25S C10H12 255S01 C11K16 256 l-HETHYL-4-(2-METHYLPROPYLBENZENE 25? 1-METHYL-1H-INDENE 258 C19H12 258501 1,2,3,4-TETRAMETHYLBENZENE 258502 C10K10 259 C11K16 260 C11H16 261 CUH16 262 C10K12 263 CUH16 264 UNKNOWN *** 255 C11H14 256 *** UNKNOWN **» 267 *** UNKNOWN *** 268 NAPHTHALENE 268501 C11K14 269 n-DODECANE 270 C11H16 271 C11H16 272 C11H14 273 C11H16 274 C13H28 ? 275 C12H18 ? 27S C12H18 277 C12K16 27B C12H16 ? 219 *** UNKNOWN *** 280 C11H14 281 C11H16 282 C11H14 283 UNKNOWN *** 284 C12H1S 285 C12H16 28€ C12H18 ? 237 C11H14 288 -** UNKNOWN *** 289 **' UNKNOWN »•* 290 •*» UNKNOWN *** 291 *** UNKNOT *** 292 C11H14 293 C11HI4 234 C12H16 235 C12H18 296 C12H18 237 C12H16 2 9B C12H16 37 ------- Aldehyde and Ketone Compound List PEAK NUMBER COMPOUND 1 Formaldehyde 2 Acetaldehydc 3 Acrolein 4 Acetone 5 Propionaldehyde 6 Crotonaldehvde 7 Butyraldehyde 8 Isovaleraldehyde 9 Valeraldehyde io' O-Tolualdehyde 11 m-Tolualdehyde 12 p-Tolualdehyde 13 • Hexanaldehyde 14 2,5-DMbenzaldehyde 15 x-Propionaldehyde 16 x-Butyraldehyde 17 x-Valeraldchydc 18 x-DMbenzaldehyde 19 x-Acrolein 20 x-Hexanaldehyde 21 x-Acetaldehydc 22 2-Butanone 38 ------- |