Characterization of Alternative Fuel Vehicle
Emissions Composition and Ozone Potential
                    Frank Black
        Atmospheric Processes Research Division
         National Exposure Research Laboratory
         U.S. Environmental Protection Agency
             Research Triangle Park, N.C.

                        and

                 Tadeusz Kleindienst
        ManTech Environmental Technology, Inc.
             Research Triangle Park , N.C.
              U.S. Department of Energy
         U.S. Environmental Protection Agency
                Interagency Agreement
           DE-AI01-94CE50397 (DOE No.)
             RW89936763-01-0 (EPA No.)

                   March 5, 1996

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Characterization of Alternative Fuel Vehicle
Emissions Composition and Ozone Potential
                    Frank Black
        Atmospheric Processes Research Division
         National Exposure Research Laboratory
         U.S. Environmental Protection Agency
             Research Triangle Park, N.C.

                        and

                 Tadeusz Kleindienst
        ManTech Environmental Technology, Inc.
             Research Triangle Park, N.C.
              U.S. Department of Energy
         U.S. Environmental Protection Agency
               Interagency Agreement
           DE-AI01-94CE50397 (DOE No.)
             RW89936763-01-0 (EPA No.)

                   March 5, 1996

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Characterization of Alternative Fuel Vehicle
Emissions Composition and Ozone Potential
                    Frank Black
        Atmospheric Processes Research Division
         National Exposure Research Laboratory
         U.S. Environmental Protection Agency
             Research Triangle Park, N.C.

                        and

                 Tadeusz Kleindienst
        ManTech Environmental Technology, Inc.
             Research Triangle Park , N.C.
              U.S. Department of Energy
         U.S. Environmental Protection Agency
               Interagency Agreement
           DE-AI01-94CE50397 (DOE No.)
             RW89936763-01-0 (EPA No.)
                DOE Program Officer
                  Michael Gurevich
                   March 5,1996

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                                          Preface
There has been considerable effort in recent years to develop and introduce transportation technology
alternatives to classical petroleum based technologies. Motor vehicles optimized for a variety of alternative
fuels such as alcohol (methanol, ethanol), compressed natural gas (methane), low pressure gas (propane), and
electricity are being introduced.  Additionally, conventional gasoline and diesel fuels are being reformulated
to provide more environmentally favorable compositions. There are several motives for these activities
including energy security and improved air quality. Air quality improvements have focused on reduction of
summer ozone, winter carbon monoxide, and toxic compounds (e.g., benzene, formaldehyde, acetaldehyde,
and 1,3-butadiene).

Quantifying changes in risk to public health and welfare associated with introduction of alternative
transportation technologies provides many complex research challenges. Emissions associated with
production, distribution, and use of the fuels must be described; multimedia (soil, water, air) fate or transport
and transformation of the emissions must be understood; human and ecosystem exposures must be
characterized; and health and welfare effects must be understood to characterize risk and options for risk
reduction. The U.S. Environmental Protection Agency (EPA) and Department of Energy (DOE) have long-
standing mutual interests in advancing knowledge of the potential air quality implications of transportation
fuel alternatives. The EPA Atmospheric Processes Research Division (APRD) of the National
Exposure Research Laboratory (NERL), in cooperation with DOE under Interagency Agreement No. DE-
MO 1-94CE50397, is characterizing emissions from alternative fuel motor vehicles and assessing their
potential  to influence ozone and toxics air quality.  This cooperative activity is mandated by the Alternative
Motor Fuels Act of 1988. The program includes assessments of emissions from conventional gasoline fueled
vehicles,  flexible fueled vehicles (FFV) configured for blends of methanol and/or ethanol with gasoline, and
compressed natural gas fueled vehicles.

The authors wish to acknowledge the review and comment of Michael Gurevich, DOE, and Brent Bailey,
National Renewable Energy Laboratory (NREL); and the technical contributions of William Crews and
Richard Snow (project supervision), Kimberly Wood and Marc Stern (analytical chemistry), Ned Perry and
Jerry Faircloth (test cell and vehicle operations), and Eric Corse (irradiation chamber operations), all of
ManTech, Inc.

The U.S.  Environmental Protection Agency through its Office of Research and Development partially funded
aind collaborated in the described research under Interagency Agreement RW89936763-01-0 from the
Department of Energy. It has been subjected to Agency review and approved for publication. Mention of
trade names or commercial products does not constitute endorsement or recommendation for use.

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                                        Summary
 The Alternative Motor Fuels Act (AMFA) of 1988 requires the Department of Energy (DOE) to purchase
 alternative fuel motor vehicles for use in government fleets, and further requires DOE to cooperate with the
 Environmental Protection Agency (EPA) and the National Highway Traffic Administration to evaluate
 potential safety, fuel economy, and emissions implications of these alternative technologies. EPA and DOE
 initiated cooperative study of alternative fuel vehicle emissions and their implications for air quality in 1991.
 The current program is being administered under a 5 year Interagency Agreement that began in 1994. The
 program is structured to provide exhaust and evaporative emissions characterization with AMFA fleet
 vehicles using a variety of fuels including 1990 industry average unleaded gasoline (RFA), reformulated
 gasoline (RFG), methanol (M85), ethanol (E85), and compressed natural gas (CNG),  under a variety of
 transient driving scenarios including the certification Urban Dynamometer Driving Schedule (UDDS) of the
 Federal Test Procedure (FTP), and a high speed, high acceleration rate "off-cycle" sequence (REP05). The
 implication of fuel differences for atmospheric ozone and toxics is examined using Carter Reactivity
 calculations and chamber irradiations of the actual vehicle emissions.  Both indoor (using an array of
 fluorescent lights to simulate sunlight) and outdoor (using natural sunlight) irradiations are included in the
 research program. The general program goal is to develop and apply test protocols for estimating the
 potential impact of changes in transportation fuels on vehicle emissions and associated atmospheric ozone
 and toxics.

 This report provides 1995 program results. Test vehicles included a 1995 conventional fuel Dodge Caravan
 and a similar 1994 vehicle designed for dedicated use of CNG fuel, a  1993 Ford Taurus and a 1993 Dodge
 Spirit designed for flexible mixtures of methanol and gasoline (0 to 85% methanol), and a 1993 Chevrolet
 Lumina designed for flexible mixtures of ethanol and gasoline (0 to 85% ethanol). Both exhaust and
 evaporative emissions are examined in close accord with the FTP, and exhaust emissions are also examined
 with a high speed, high acceleration rate "off-cycle" driving schedule (REP05). The UDDS cycle of the FTP
 has a maximum speed of about 57 mph, maximum acceleration rate of about 3.3 mph/sec, and average speed
 of about 19.6 mph.  The REP05 cycle has a maximum speed of about  80 mph, maximum acceleration rate of
 about 8.5 mph/sec, and average speed of about 51.5 mph, with high speed modes reported as REP05-1 and
 high acceleration rate modes as REP05-2. This represents a rather limited test matrix (the number of vehicles
 and fuels examined limited by available resources), and the observations and conclusions may not be
 representative of the specific technologies.  However, when examined with a number of similar studies, this
 program will contribute to collective conclusive observations.

The atmospheric chemistry of the exhaust emissions is examined using 12 h indoor irradiations in an 8000 L
chamber with reactive organic gases (ROG, ppmC) to oxides of nitrogen (NOX, ppm) concentration ratios of
about 5.5, ratios that accentuate differences in organic reactivity. These conditions are consistent with
examining the potential to influence atmospheric ozone by changing the composition of organic precursors.
A mixture of blacklight fluorescent and UV chamber bulbs is selected to match, to the extent possible, solar
radiation between 300 and 400 nm. The major criteria for the spectral match are a photolysis rate for NO2
similar to that which occurs at midlatitudes during the summer (i.e., 0.3 - 0.5 min'1) and an accurate
photolysis rate for carbonyl compounds relative to that for NO2. Quantitative transfer of emissions from the
vehicle to the irradiation chamber is assured. Initial chamber ROG concentrations are about 2.2 ppmC with
NOX concentrations about 400 ppb. Although these concentrations are higher than typical of urban
environments, they are consistent with the chamber conditions necessary to provide reasonable test accuracy
and precision (e.g., minimizing the relative importance of chamber wall effects and the uncertainty of
analytical measurements).

Atmospheric ozone does not result from the reaction of emissions from a single source, but from the reaction
of a composite mixture of emissions from many different sources in the airshed. The propensity of emissions

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 from a selected source to form ozone is generally examined by injecting the emissions into organic and
 nitrogen oxide mixtures representative of the airshed of interest. Such determinations with individual organic
 components have been conducted to establish incremental reactivities (e.g., Carter Maximum Incremental
 Reactivity). To date, few experiments have been conducted by injecting exhaust or emissions mixtures into a
 hydrocarbon surrogate mixtures representative of potential future airsheds. Future airsheds will likely have
 different organic profiles than current airsheds (or past airsheds) as a consequence of changing fuels and
 emissions control technology.

 Irradiation chamber studies of the ozone implications of changes in vehicle fuels can be run using varied
 degrees of substitution of urban (surrogate) ROG with fuel specific vehicle exhaust, observing differences in
 chamber ozone (and other compounds) concentration profiles versus time. The classical "base-case" urban
 (surrogate) ROG compositional profile used for this purpose is very similar to baseline gasoline exhaust
 composition. The "base case" urban surrogate to which exhaust organics are typically added in irradiation
 chamber studies of the ozone implications of alternative fuels has been based on 6-9 AM organic data
 developed in studies of air quality in 29 U.S. cities during the 1984 to 1988 calendar period. Examination of
 this data strongly suggests the dominant influence of motor vehicle exhaust (the morning to-work commute).
 Motor vehicle exhaust is strongly influenced by fuel composition.  In this program, 100% alternative fuel
 vehicle technology substitution is assumed to maximize observed fuel to fuel differences. It is assumed that if
 the alternative fuel vehicles of interest are substituted for all baseline gasoline vehicles, urban surrogate will
 have a compositional profile similar to that of the alternative fuel vehicle exhaust.

 Contrasting the FTP exhaust emission performance of the varied vehicles with different fuels: nonmethane
 organic gas (NMOG), CO, and NOX emission rates (g/mi) are lower for the Dodge Caravan with CNG fuel
 (0.006,0.54, and 0.02, respectively) than with RFG fuel (0.15,1.70, and 0.29, respectively); NMOG and CO
 emission rates are higher for the Lumina with E85 fuel (0.24, and 3.19, respectively) than with RFG fuel
 (0.14 and 1.97, respectively), but NOX rates are lower (0.18 with E85, and 0.27 with RFG); NMOG and CO
 emission rates are higher for the Spirit with M85 fuel (0.28 and 5.13, respectively) than with RFG fuel (0.15
 and 3.36, respectively); and NMOG, CO, and NOX  emission rates are higher for the Taurus with M85 fuel
 (0.30, 2.48, and 0.24, respectively) than with RFG fuel (0.12,1.44, and 0.18, respectively). In each case,
 exhaust NMOG and CO emission rates are higher with the alcohol fuels than with RFG fuel. It is interesting
 to note that the Dodge Caravan emission rates with CNG fuel are well below the California Ultra Low
 Emissions Vehicle (ULEV) standards of 0.040 g/mi NMOG. 1.7 g/mi CO, and 0.2 g/mi NOX. CO and NOX
 emission rates  are generally elevated by the high acceleration rate REP05-2 driving scenario. For all vehicles
 except the Dodge Caravan, the CO emission rates are more than an order of magnitude higher for the
 REP05-2 schedule than the FTP schedule.

 Excluding the CNG Caravan with no evaporative emissions, evaporative emissions  accounted for 34% to
 84% of vehicle total FTP NMOG emissions. Generally, evaporative emission rates are lower with the
 alternative fuel (CNG, M85, E85) than with RFG fuel (excepting the Spirit). Evaporative NMOG emission
 rates (g/mi equivalent) for the Taurus are 0.61 g/mi with RFG fuel and 0.36 g/mi with M85 fuel; for the
 Lumina 0.18 g/mi with RFG fuel and 0.13 g/mi with E85 fuel; and for the Spirit 0.16 g/mi with RFG fuel and
 0.19 g/mi with M85 fuel.

 The ozone potential (g ozone per mile driven) of the FTP emissions (combined exhaust and evaporative),
 estimated using Carter Maximum Incremental Reactivity (MIR) calculations, is generally similar for the
 alcohol alternative fuels (M85 and E85) and reformulated gasoline (RFG), but significantly reduced with
 CNG fuel. In this program, RFG emissions ozone potential ranged from 0.97 to 1.73 g O3/mi (average 1.18,
n=4), M85 emissions ozone potential from 0.94 to 1.15 g O3/mi (average 1.05, n=2), E85 emissions ozone
potential 0.95 g O3/mi (n=l), and CNG emissions ozone potential 0.05 g O^fmi (n=l). With the alcohol
fuels (M85 and E85), the increased ozone potential of the exhaust emissions relative to RFG exhaust

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 emissions is offset by the reduced ozone potential of the evaporative emissions relative to RFG evaporative
 emissions. With CNG fuel, evaporative emissions are essentially eliminated and exhaust ozone potential
 dramatically reduced relative to RFG exhaust emissions.  The MIR specific reactivities (g ozone per g emitted
 NMOG) of CNG, E85, and M85 exhaust emissions relative to that of RFG were about 0.9,0.7, and 0.4,
 respectively; and of E85 and M85 evaporative emissions relative to that of RFG about 0.6 and 0.7,
 respectively. Exhaust ozone potential is elevated by REP05-2 high acceleration rate driving conditions
 relative to FTP conditions with the liquid fuels.

 With the exception of CNG, FTP toxic emissions (sum of benzene, 1,3-butadiene, formaldehyde, and
 acetaldehyde) are elevated by the alternative fuels relative to that with RFG fuel. With RFG fuel the toxic
 compound emission rates ranged from 10.9 to 14.5 mg/mi, with E85 fuel the toxic compound emission rate
 was 25.9 mg/mi, with M85 fuel the toxic compound emission rates ranged from 17.9  to 19.4 mg/mi, and
 with CNG fuel the toxic compound emission rate was 0.8 mg/mi. The increase is associated with elevated
 formaldehyde emission rates with M85 fuel, and elevated acetaldehyde with E85 fuel.  A dramatic change in
 toxic emissions composition is observed with the REP05-2. Benzene emission rates increased substantially,
 becoming the dominant toxic with all fuels except CNG.  Excluding the Dodge Caravan data (for both RFG
 and CNG fuels), with little evidence of power enrichment during the REP05-2, benzene emission rates varied
 from 54 (Spirit) to 163 mg/mi (Lurnina) with RFG fuel, and from 19 (Lumina, E85) to 30 mg/mi (Taurus,
 M85) with the alcohol alternative fuels.

 Energy efficiencies are improved for all vehicles with the alternative fuels relative to RFG.  Resulting from
 net improved efficiencies and reduced energy contents (BTU/gal) of the alcohol fuels, volumetric mpg fuel
 economies are reduced about 23% with E85 fuel compared to RFG, and about 39% with M85 fuel compared
 to RFG fuel.

 This years chamber studies are focused on the ozone potential of vehicle exhaust emissions. With motor
 vehicle exhaust the ROG (ppmC)/NOx (ppm) ratio is typically lower than the target initial chamber condition
 of 5.5, especially so after initiation of catalytic emissions control. The ratio is maximized in this program by
 collecting exhaust during the initial 124 s of the FTP cold start.  The composition of integrated transient
 vehicle organic emissions is dominated by emissions occurring during this "cold start" period and during
 events (high acceleration power enrichment, varied engine and/or control system malfunctions) resulting in
 fuel rich combustion. The MIR specific reactivity of the 124 s sample is very similar to the weighted FTP
 value. ROG surrogates of the exhaust are added, when necessary, to increase the ROG (ppmC)/NOx (ppm)
 ratio to 5.5. The atmospheric photochemistry of vehicle exhaust emissions and/or associated surrogates is
 examined using 12 h chamber irradiations with RFG, M85, E85, and CNG fuels. Time resolved
concentration profiles of nitric oxide (NO), nitrogen dioxide (NO^, ozone (O3), peroxyacetylnitrate (PAN),
 formaldehyde (HCHO), acetaldehyde (CH3CHO), and other carbonyls are presented. Carter maximum
 incremental reactivity (MIR) based specific reactivity (i.e., mg O3/mg NMOG, CO, and CH4), chamber 12 h
ozone concentration, and dNO/dt at chamber NO-NO2 concentration crossover suggest that RFG exhaust
ozone reactivity ~ E85 exhaust ozone reactivity > M85 exhaust ozone reactivity > CNG exhaust ozone
reactivity per unit of NMOG, CO, and CH4 mass emissions.  Under the program test conditions (i.e.,
 vehicles, fuels, and driving scenarios), the ozone reactivity of CNG exhaust (NMOG, CO, and CH4) is about
 1/5  that of RFG and E85 exhaust (NMOG, CO, and CH4); and the ozone producing potential of M85 exhaust
 (NMOG, CO, and CH4) is about 1/2 that of RFG and E85 exhaust (NMOG, CO, and CH4). Observed
 chamber toxic compound concentrations after 12 h exhaust irradiations included PAN substantially lower
 with M85 (2.2 ppbv) and CNG (1.2 ppbv) fuels than with RFG (20.4 ppbv) and E85 (24.5) fuels, and
 acetaldehyde substantially higher with E85 (68.3 ppbv) fuel than RFG (16.5 ppbv), M85 (5.1 ppbv), or CNG
 (10.9 ppbv) fuels, and formaldehyde higher with E85 (105 ppbv) and CNG (97.5 ppbv) fuels than with RFG
(65.1 ppbv) and M85 (67.5) fuels.

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The photochemistry of exhaust surrogates is also examined in this program. For the liquid fuels, the
surrogates are organic mixtures based on vaporization of whole fuel with addition of ethylene, propylene,
formaldehyde, and/or acetaldehyde; and for CNG fuel, a mixture of 7 organics approximating the major
component relative concentrations of the exhaust. Surrogate addition is necessary with RFG and CNG
exhaust to attain target initial chamber ROG/NOX concentration ratios. Contrasting the surrogate 12 h ozone
concentrations and crossover dNO/dt reactivity parameters with those observed during the associated
exhaust irradiations indicates that the fuel surrogate ROG may not have been as reactive as the exhaust ROG
(i.e., 12 h ozone concentrations were less than expected, and dNO/dt slopes less than expected). The
combustion product organics may not be adequately represented by the surrogates.  However, the observed
differences in 12 h ozone concentrations are not suggested by differences in Carter MIR specific reactivities
for the exhaust and associated surrogates. Differences in initial chamber water concentrations may also have
contributed to some of the observed differences. The surrogate chamber tests were conducted without water
added to simulate that associated with diluted auto exhaust. This could have reduced OH radical
concentrations (resulting from O3 + hv - O('D) + O2, O('D) +H2O-  2OH) after chamber NO is depleted. In
this latter case, the actual exhaust runs would not have been compromised since the surrogate exhaust ROG
was added to actual exhaust, including water vapor. The surrogate uncertainties will be further studied during
the 1996 program.

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                                Table  of Contents
 Preface	3

 Summary  	4

 List of Figures	9

 List of Tables	9

 Introduction	 10

 Experimental	 13

       Emission Characterization	 13
              Facilities	 14
              Vehicle/Evap Canister Preconditioning	 14
              Exhaust emissions determination	 14
              Evaporative emissions determination	 19
       Irradiation Chamber Studies  	 19
              Facilities	20
              Photochemical measurements	22

 E.esults and Discussion  	24

       Emissions Results  	24
              Observations with FTP Driving Simulations	25
              Observations with REP05 Driving Simulations  	30
              Fuel Economy	33
       Irradiation Chamber Assessments	33
              Chamber Qualifications	33
              Experimental Observations  	34

Comparison of Results with Other Studies	38

Conclusions	42

References	43

Glossary	47

APPENDICES

       A. Test Fuel Composition
       B. Ozone Potential (Carter MIR)
       C. Detailed Emissions Composition and Carter Ozone Reactivity Summaries
       D. Chamber Initial Conditions, Observed 12h Reaction Products, and Reactivity Parameters for
          Irradiations of Exhaust and/or Surrogate Samples for RFG, M85, E85, and CNG Fuels
       E. Time Resolved Profiles of Chamber O3, NO, and NO2(NOX - NO) Concentrations for
          Irradiations of Exhaust and Surrogate Samples for RFG, M85, E85, and CNG Fuels
       F. Time Resolved Profiles of Chamber PAN and Carbonyl Compound Concentrations for
          Irradiations of Exhaust and Surrogate Samples for RFG, M85, E85, and CNG Fuels

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                                   List of  Figures
Figure 1        Federal Test Procedure emissions test sequence	 16
Figure 2        Test cell configuration 	 17
Figure 3        Transient driving schedules	 18
Figure 4        Photochemical chamber configuration	20
Figure 5        Fluorescent lights spectral distribution  	21
Figure 6        FTP ozone potential (Carter MIR)	27
Figure7        FTP NMOG specific reactivity (Carter MIR)	27
Figure 8        CNG exhaust MDR. Specific Reactivity vs NMOG emission rate	28
Figure 9        FTP toxic compound emissions	29
Figure 10       FTP MTBE emissions 	30
Figure 11       REP05 ozone potential (Carter MIR)  	31
Figure 12       REP05 NMOG specific reactivity (Carter MIR)	31
Figure 13       REP05 toxic compound emissions	32

                                   List of Tables

Table 1        Test vehicle specifications	 14
Table 2        Test fuel specifications	 15
Table 3        Regulated emissions	24
Table 4        FTP exhaust and evaporative NMOG and OMHCE emissions	26
Table 5        FTP NMOG MIR specific reactivity ratios	28
Table 6        Fuel economy	33
Table 7        Irradiation chamber run summary  	34
Table 8        Surrogate compositions 	35
Table 9        Ozone reactivity parameter summary	36
Table 10        Toxic compound concentrations after 12 h exhaust irradiations	38
Table 11        Comparison of results with other studies 	40

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                                       Introduction

 Many urban areas in the United States continue to be plagued with ozone concentrations that exceed the
 National Ambient Air Quality Standard (NAAQS). As a result, large populations are exposed to ozone levels
 leading to well documented adverse effects (Watson, et al., 1988). Unlike most regulated pollutants, ozone is
 not emitted directly, but is produced in the atmosphere by secondary photochemical processes. Thus,
 regulating ambient ozone cannot simply involve limiting its emissions.  It has only been during the last 25
 years that an understanding of the general mechanism for ozone formation in the polluted troposphere has
 evolved. It is well known that ozone is formed through a nonlinear process involving reactive organic gases
 (ROGs) and oxides of nitrogen (NOx)(Bowman and Seinfeld, 1994a). Thus, limiting ambient ozone
 necessarily involves regulating chemical precursor emissions.

 The U. S. Congress directed attention to the development and introduction of alternative transportation fuels
 in the 1988 Alternative Motor Fuels Act (U. S. Congress, 1988); and further emphasized the development of
 this technology, as well as reformulation of petroleum-based gasoline and diesel fuels to more
 environmentally favorable compositions, in the 1990 Clean Air Act Amendments (U. S. Congress, 1990).
 Goals for this legislation included improved ozone, CO, and toxics air quality. The complexity of the
 associated issues has long been recognized and the subject of much research (National Research Council,
 1991). Since ozone is produced in ambient ROG-NO, systems by a complex series of reactions involving
 ROGs, NOX, and UV  sunlight, rational decisions on regulating either or both of the precursor emissions relies
 on fundamental understanding of the details of the ozone formation mechanism. Recently summarized
 "Research Needs" for evaluation of the potential impact of alternative transportation fuels on ozone and other
 toxic air pollutants include quantification of vehicle tailpipe, evaporative, and running-loss mass emission
 rates and chemical compositions with "real-world" vehicles, fuels, and driving scenarios; and development
 and evaluation of chemical  mechanisms for predicting the atmospheric transformations by which emitted
 pollutants contribute to ozone and other secondary pollutants (Atkinson, et.al.,1988; Black,  1992; Carter,
 etal., 1994).

 The Alternative Motor Fuels Act of 1988 requires that DOE purchase alternatively fueled motor vehicles for
 use in government fleets, and further requires that DOE cooperate with EPA and the National Highway
 Traffic Administration to evaluate potential safety, fuel economy, and emissions implications of these
 alternative technologies.  EPA and DOE initiated cooperative study of emissions from these vehicles and
 their implications for air quality in 1991.  The historical progress of these studies is documented in several
publications (Black and Kleindienst,  1992; Gabele and Black, 1993; Kleindienst, et. al., 1994; Gabele, 1994;
 and Gabele,  1995).  This report provides results from calendar year 1995 studies.

The largest study characterizing changes in motor vehicle emissions with changes in fuel composition, and
the implications of these changes for ozone and toxics air quality was undertaken by the automotive and
petroleum industries, beginning in 1990, in the Air Quality Improvement Research Program (AQIRP).
General Motors, Ford, Chrysler, and 14 petroleum companies participated in this program. Results have
been published in a series of Technical Bulletins (15 in number as of July, 1995)  by the Coordinating
Research Council (CRC, 1990-95), and also in the literature of the Society of Automotive Engineers (SAE,
 1991-95). The California Air Resources Board (CARB) has actively examined emissions from alternative
fueled motor vehicles in their attempt to provide Reactivity Adjustment Factors (RAF) for implementation of
emission standards for alternative vehicle-fuel technologies providing uniform ozone benefit (i.e., similar
 ozone reduction with varied organic emissions profiles) (Croes, etal., 1992; CARB, 1995).  For example, a
 fuel with a RAF of 0.5 would be permitted twice the mass emission rate of the base fuel.  The DOE has
 sponsored a number of research programs examining the potential for alternative fuels to abate ozone and
toxic air pollution (Bailey, 1994). There have been many other studies of alternative fuels issues by
government, industry, and academia, beyond the scope of this report for comprehensive citation (Chang and

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 Rudy, 1990; Black, 1991; Black and Gabele, 1991; Black, 1992; Gabele and Black, 1993; Gabele, 1994;
 Hoekman, 1992; etc.). Although the literature suggests potential for air quality benefits relative to baseline
 gasoline (1990 industry average) for reformulated gasolines and methanol/ethanol-gasoline blended fuels, it
 appears that compressed natural gas offers the most significant potential for reduction of ozone precursor
 and toxic emissions from Otto cycle motor vehicle engines (AQIRP, 1995; Gabele, 1994; Geiss, et.al., 1992).

 Irradiation chamber study designs are based on understanding of the atmospheric photochemical processes
 producing ozone. On a molecular basis, ozone (O3) is formed in the lower atmosphere by photolysis of
 nitrogen dioxide (NO2), also generating nitric oxide (NO). The three compounds (NO, NO2, and O3) form a
 photostationary state according to the following reactions:

                                       NO2 + hv -NO
                                           O + O2 - O3
                                       03 + NO ~
In the absence of organic compounds, the steady-state ozone concentration would depend only on the
intensity of radiation (hv) and the ratio NO/NO2. The presence of ROGs in an airshed permits NO2 to be
generated through the oxidation of NO by organic radicals, rather than by reaction with O3. Thus, O3 can
build up as long as there is NO2 being photolyzed.

An essential aspect of ozone control is fundamental understanding of the major processes for oxidation of
ROGs in the presence of NOX. The initial step in the mechanism is typically reaction of the organic
compound with hydroxyl radical. In the presence of oxygen, the initial radical is converted into a peroxy
radical that reacts with nitric oxide (NO) under urban conditions.  Although the reaction yields a small
amount of organic nitrates, the predominant path is to oxidize NO to NO2 and form an alkoxy radical. The
alkoxy radical generally decomposes or reacts with oxygen to form an aldehyde or ketone and the
hydroperoxyl radical (HOj), although isomerization is also possible for long chained paraffinic hydrocarbon
precursors. Decomposition products from the alkoxy radical reactions lead to organic radicals that can also
read: with O2 to give HO2. Under urban conditions HO2 is rapidly converted to OH through reaction with
NO.  This cyclic process to convert HO2 to OH is essential to sustain the photochemical process. The
reaction cycle will continue for as long as there is radiation and available NOX. While NO2 can be
regenerated through  the reactions shown above, it can also be removed from the reactive system through
termination reactions. These reactions form organic  nitrates (e.g., peroxyacetyl nitrate) and nitric acid.

While the general photochemical mechanism for the  atmospheric  degradation of ROGs is known, detailed
chemical mechanisms for some classes or organic constituents, such as aromatic hydrocarbons, are poorly
understood.  Thus, it is extremely difficult, if not impossible, to predict ozone concentrations purely on
mechanistic principles. As a result, parameterization approaches have been used to  determine changes in
ozone concentration  due to changes in ROG and NOX levels (e.g., ozone isopleth diagrams).

The peak formation of ozone in a complex airshed is frequently described in terms of an isopleth diagram that
shows ozone for a wide range of ROG to NOX ratios. The isopleth gives the direction and magnitude of the
change in ozone concentration that occurs due to changes in either the ROG or NOX concentrations. In
general, under low to moderate ROG/ NOX ratios (i.e., <15), decreasing ROG concentrations decreases ozone
concentrations; however, under high ROG/ NOX ratios (i.e., >30), ozone concentrations can be highly
insensitive to changes in the ROG levels (National Research Council, 1991). Reducing NOX concentrations
can lead to an increase, a decrease, or no change in ozone concentrations depending  upon where on the
isopleth diagram (i.e., the ROG/NOX ratio) the change occurs. While the isopleth diagram is designed to
predict peak ozone concentrations, it does not predict where in the airshed the maximum occurs.  Such
predictions are generally based on three dimensional airshed models (Russell, et al,  1991).


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 Isopleth diagrams have been the basis for "roll back" of hydrocarbons to reduce ozone. This approach does
 not distinguish between hydrocarbons or hydrocarbon classes, as the rollback formula is based only on mass.
 However, it is well known that degradation rates of individual hydrocarbons can vary substantially in the
 atmosphere. Both kinetic and mechanistic considerations are crucial for determining the relative importance
 of different organics (e.g., alkanes, alkenes, aromatics, aldehydes) to ozone air quality, as is the environment
 in which the ROGs degrade (Bowman and Seinfeld, 1994b). These considerations have led to development
 of reactivity schemes for evaluating the relative importance of individual ROGs to ozone formation.

 While a number or reactivity schemes have developed over the years, a recent scheme by Carter is the most
 widely used (Carter and Atkinson, 1987; Lowi and Carter, 1990; Carter, 1994). The reactivity scale
 developed by Carter recognizes that the ability of a single organic compound to produce ozone depends upon
 the rate at which the compound initially reacts (usually with hydroxyl radicals), the mechanism of its
 decomposition, and the characteristics of the environment into which the compound is emitted. This
 environment is typically referred to as the "base case." The base case ROG represents a composite mixture
 of initial ROGs from all sources in the reaction scenario. Reactivity factors for a number of scenarios (i.e.,
 airshed environments) have recently been developed. The two scales most frequently used are the Maximum
 Incremental Reactivity (MIR) scenario and the Maximum Ozone Reactivity (MOR) scenario. The  MIR scale
 is used where the ROG input (i.e., the organic compound emission rate and composition) has the maximum
 incremental effect on ozone formation. The MIR scale is most relevant for urban scenarios where the airshed
 is relatively NOX rich, such as the  Southern California airshed. The California Air Resources Board has
 recently adopted the MIR scale as  the basis for developing fuel specific reactivity adjustment factors (RAFs)
 permitting ozone potential comparisons for emissions from different technologies (Croes, et.al., 1992;
 CARB, 1994).  In this method, the mass emission rate of each constituent is reactivity weighted to obtain the
 constituent's propensity for ozone formation. The reactivity weighted mass emission rates are then summed
 to estimate the ozone potential of the exhaust mixture. This approach provides the basis for California's fuel
 neutral regulations encouraging marketplace competition of alternative and reformulated fuels (which tend to
 have lower ozone reactivities) with conventional fuels.

 Photochemical mechanisms for atmospheric reactions are typically used to calculate ozone formation
 potentials, and associated reactivity scales (e.g., MIR and MOR). The initial experimental basis for obtaining
 reactivities  comes from studies of NO oxidation with hydrocarbons incrementally added to a surrogate base
 case organic mixtures. Results with selected hydrocarbons are then used to test the mechanism and to help
 "calibrate" the scale in terms of mass of ozone formed per incremental mass of hydrocarbon added  to the base
 mixture. Only a small fraction of individual constituent organic compounds have been tested experimentally
 with selected base case mixtures. Moreover, these simple tests have been conducted in only a few
 laboratories. Thus, although the practice of using MIR based RAFs to predict the ozone potential of exhaust
 mixtures from various  fuels is widespread, considerable experimentation is required to confirm that such
predictions are valid with real exhaust mixtures (Yang, etaL, 1995).

Evaluations have been attempted by making comparisons of algebraic relative reactivities (e.g., Carter MIR)
with relative reactivities obtained using airshed models (McNair, et.al., 1994; Russell, et.al., 1995), and
irradiation chamber observations (Jeffries and Sexton, 1995; Kelly, et.al., 1994; Kelly and  Wang, 1995).
Although agreement is good for individual NMOG species, deviations to ±15 percent are suggested with
complex mixtures in airshed  model comparisons. Jeffries chamber data with surrogate mixtures (30-50
compounds) suggested different relative reactivities for industry  average gasoline (IAG) and M85 than that
calculated using Carter MTR (M85/IAG - MIR 0.86, chamber 0.6). Kelly (Environmental Research
Consortium) has initiated a program to make MER-chamber comparisons with whole exhaust mixtures.  The
results examined in this report make similar comparisons with different vehicles, fuels, and facilities.

The "base case" urban  surrogate to which exhaust organics are incrementally added in irradiation chamber


                                               12

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 studies of the ozone implications of alternative fuels has typically been based on 6-9 AM organic data
 developed in studies of air quality in 29 U.S. cities during the 1984 to 1988 calendar period.  Examination of
 this data strongly suggests the dominant influence of motor vehicle exhaust (the morning to-work commute).
 Motor vehicle exhaust is strongly influence by fuel composition. Although this "base case" may be suitable
 for examining ozone chemistry in atmospheres dominated by gasoline associated emissions, assessment of
 the maximum potential to influence ozone with alternative fuels suggests 100% substitution of gasoline
 emissions with emissions associated with the fuel of interest, i.e., the urban air surrogate would have a
 different organic profile if all gasoline vehicles were replaced by M85, E85, or CNG vehicles. The organic
 mixtures examined in  the irradiation chamber study reported in this document were wholly based on the fuels
 of interest.

 Atmospheric ozone does not result from the reaction of emissions from a single source, but from the reaction
 of a composite mixture of emissions from many different sources in the airshed.  The propensity of emissions
 from a selected source to form ozone is generally examined by injecting the emissions into hydrocarbons and
 nitrogen oxides representative of the airshed of interest. Such determinations with individual organic
 components have been conducted to establish incremental reactivities (Carter and Atkinson, 1987; Kelly et
 al, 1993). To date, few experiments have been conducted by injecting exhaust or emissions mixtures into a
 hydrocarbon surrogate mixture representative of potential future airsheds. Future airsheds  will likely have
 different organic profiles than current airsheds (or past airsheds) as a consequence of changing fuels and
 emissions control technology. There are several difficulties with such an approach, not the least of which is
 forecasting the characteristics of future airsheds.  The experiments of this study examine ozone formed during
 iiradiation of motor vehicle emissions in atmospheres strongly impacted by the vehicle-fuel technologies
 being examined.  While this approach may be less representative of .the present-day implications of the fuels
 being studied, the research is designed to consider the maximum potential impact in urban atmospheres where
 the alternative vehicle-fuel technologies dominate the fleet and the atmospheric organic profiles. The results
 can be used to examine the extent to which revisions may needed to incremental reactivity factors  as urban air
 compositions change.
                                      Experimental
The reported study was conducted at the EPA, National Exposure Research Laboratory (NERL) located in
Research Triangle Park, N.C. Exhaust and evaporative emissions are characterized using laboratory driving
simulation test protocols with a variety of alternative recent model year vehicle-fuel technologies; and the
atmospheric photochemistry of the emissions is examined using irradiation chamber test protocols.  Test
vehicles included a 1995 conventional fuel Dodge Caravan and a similar 1994 vehicle designed for dedicated
use of CNG fuel, a 1993 Ford Taurus and a 1993 Dodge Spirit designed for flexible mixtures of methanol
and gasoline (0 to 85% methanol), and a 1993 Chevrolet Lumina designed for flexible mixtures of ethanol
and gasoline (0 to 85% ethanol). Test vehicle specifications are provided in Table 1. Test fuel specifications
are provided in Table 2. Full organic compositional profiles for each fuel are provided in Appendix A.

Emissions Characterization

Both exhaust and evaporative tests are conducted in close accord with the Federal Test Procedure (FTP)
(Code of Federal Regulations, 1992; Federal Register, 1993), except that a high speed, high acceleration rate
"off-cycle"  sequence (REP05) is examined in addition to the certification Urban Dynamometer Driving
Schedule (UDDS).  Figure 1 provides a general schematic of the FTP sequence. The optionable evaporative
emissions test procedure, examining diurnal emissions for 48 hours and hot soak emissions with the test cell
at 68-86 °F, is used in this program. The REP05 exhaust test sequentially follows the FTP.

                                                13

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                               Table 1. Test Vehicle Specifications.
     Vohiclo       Engine       Fuol      Emission    Ml/oago     Inortia Wt.     HP @
                                Systom      Controls                                so mph

   1995 Dodgo   3.3 L/V-6      MPFI      CAT/EGR     13,596       3,875         1O.O
   Caravan
   (Conv.)

   1993 Taurus   3.O L/V-6      MPFI      TWC/O2S/    16,996       3.625         6.BO
   FFV (MBS)                    (FFV)        EGR


   1993 Dodgo  2.S L/L-4      MPFI      CAT/EGR     24,039       3.2GO         8.4O
   Spirit FFV                    (FFV)
   (M86)


   1993          3.1 L/V-6      MPFI      CAT/EGR     17.7OO       3,76O         6.6O
   Lumlna                       (VFV)      TWC/O2S
   VFV (£85)


   1994 Dodgo  3.3 L/V-6       Fl        CAT/EGR     5.O28        3.875         1O.O
   Caravan                     (CNG)
   (CNG)
Facilities

A Burke Porter, Reliance DC electric chassis dynamometer, with 9.5 in. diameter mechanically coupled rolls,
is used for motor vehicle road-load simulation. Vehicle tire pressure is maintained at 45 psi to minimize heat
buildup and associated changes in tire rolling resistance.  The dynamometer accurately simulates inertia from
1,500 to 5,500 pounds during vehicle acceleration-deceleration driving modes, and also aerodynamic drag
and frictional losses as a function of speed.  The engine exhaust is sampled using a Horiba Constant Volume
Sampling (CVS) system. Evaporative emissions are characterized using a 24 h, multi-day diurnal (72 to 96 to
72 °F) Sealed Housing for Evaporative Determination (SHED).  The SHED is of the "fixed volume" type,
equipped with a constant flow system (i.e., with filtered activated carbon inlet and flow controlled exit) to
accommodate SHED gas volume "changes" associated with procedural temperature ramps. The SHED
internal-external barometric pressure differential does not exceed 2 in. water.  Vehicle exhaust is transferred
to the irradiation chamber via a heated (150 °F) pump and tubing. All sample handling equipment and
procedures  are quality assured by injecting known amounts of "at risk compounds" into the exhaust at the
tailpipe exit and following transfer to the irradiation chamber. Figure 2 provides a schematic of the chassis
dynamometer test cell equipment, and Figure 3 illustrates the program transient driving cycles.

Vehicle/Evap Canister Preconditioning

A major goal of this program is assessment of the impact of varied fuel formulations on motor vehicle
emissions.  To assure that fuel memory effects are minimized, each vehicle is preconditioned with the test fuel
prior to emissions evaluation as illustrated in Figure 1 (Federal Register, 1993).  When a vehicle is tested
with multiple fuels, a supplemental conditioning sequence is completed prior to the FTP sequence to assure
that vehicle "adaptive learning" is complete before emissions evaluation. This supplemental sequence is also
described in Figure 1.

Exhaust emissions determination

The electric chassis dynamometer used to simulate vehicle road load is enclosed within a Temperature
Controlled Test Chamber (TCTC) permitting vehicle soak and operation at prescribed temperatures.  Exhaust
gases are sampled using the constant volume sampling (CVS) techniques commonly used for vehicle


                                               14

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                                Table 2. Test Fuel Specifications.
     Spoclflca tlon
                          RFG
                                                 M-8B
                   E-8S
                                                                                  CNG
API Gravity
RVP
Sulfur, ppm
59.4
6.86
36
48.3
7.46
7.0
49.7
7.1S
13.6
    MTBE, GC vo/96

    Mothanol,  GC
    vo/96

    Ethanol,  GC
                              11.1
                                             84.4
Parafflnlc HC.
GC vo/96
(CNG. ppmc96J

Olofinlc HC,
GC vo/96
(CNG, ppmc96)
                              59.2
                              6.2
                                                 11.8
                                                 O.7
                                                                    85.3
                                                                    10.6
                                                                   O.8
                                                                                      99.8
                                                                                      0.02
    Aromatic HC, GC
    vo/96 (CNG, ppmc96)   23.5
    Unknown HC,
    GC vo/96
    (CNG, ppmc%)

    Lower Heating
    Value. BTU/gal
    Distillation,
                          O.1
                          112,239
                                            3.1
                                            0.0
66,745
                                                               3.3
                                                               O.O
82,914
                                                                                  O.14
                                                                                  0.04
                                                                                   114,216
                                                                                  gasoline
                                                                                  equivalent
IBP
7O96
5O96
9096
EP
104
144
207
294
389
119
142
147
148
152
124
164
172
172
19O
certification tests (Code of Federal Regulations, 1992). To prevent losses during sample transport, a heated
transfer tube (to 235 °F) is used within the TCTC to direct vehicle raw exhaust to the CVS dilution tunnel
where the exhaust gas is thoroughly mixed with heated diluent air (to ISO °F) (Black and Snow, 1994; Stump,
et al, 1995). Total flow through the CVS dilution tunnel is held constant at 700 CFM.  Samples of diluted
exhaust are collected directly from the dilution tunnel at a constant flow rate over the duration of the test,
permitting determination of pollutant mass emission rates (g/mi) from sample concentration and totalized
flow.

Exhaust emissions and fuel economy are determined using both the UDDS transient driving schedule, and an
"off-cycle" high speed, high acceleration rate REP05 transient driving schedule (illustrated in Figure 3).  The
UDDS cycle has a maximum speed of about 57 mph, maximum acceleration rate of about 3.3 mph/sec, and
average speed of about 19.6 mph. The FTP includes three test phases: a cold start transient phase (505 sec.),
a stabilized phase  (867 sec.), and a hot start transient phase (505 sec.). There is a 10 minute engine-off soak
period between phases two and three. Emissions from each phase are analyzed separately and then combined
                                               15

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( Start J
Fuel drain & fill
1
Vehicle soak
f
Preconditioning drive
i
Fuel drain & fill
\
Precondition canister
I
Cold start exhaust test
1
Hot start exhaust test
1
Hot soak test
68 -86 F ambient
t
Vehicle soak
*
Diurnal emission test
72 - 96- 72 F
2 heat builds in 48 hrs
X" ^ NO /
(Stmg TfttFutl?)
c
YES
i C
1 «-"»" ' 9 Engine off \
| 1 min Cj
Fuel drain & till f) „
1 	 r 	 ' V Start engine.
4 /tfto f m/n /
-L- IhrMAX S
CTO V Engine off .
• £7C- Unto <
«-s«/in | Start engine,
Idle 1 min
' (.
Y Engine off
	 ~ 5 m/n
» """"^ supplemental precon
I with fuel change
1hr
I
f 2-38 Art
1
80 m/n. canister
purge 0.8 CFM
Drain fuel
3 gal. till - new ft/a/,
<60F
Start engine, idle
1 min.
Drain fuel
) 1hr. 60-84F
diurnal heat build
}UM
preconditioning
drive
ittioning
s
Figure 1. Federal Test Procedure emissions test sequence.
                          16

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     BAG FOR
     ORGANIC
     ANALYSIS
          A
     HEATED
     HCFID
                                                                           BAGS for ORGANIC
                                                                              ANALYSIS
                    TEMPERATURE
                    CONTROLLED
                    TEST CELL
                    WITH DYNAMOMETER
              HEATED
              TRANSFER
              LINE
                    ALDEHYDE
                  CARTRIDGES

HEATED TRANSFER LINES
                               DILUTION
                                          TUNNEL
              HEATED INLET AND FILTER
       HEATED RD

HEATED TRANSFER LINE
                                                                   I
                                                                 FILTER
                                                                   TEFLON
                                                                   LINE
                                                      FTIR
                                                   ANALYZER
                                Figure 2. Test cell configuration.
 using a weighting formula to produce a composite FTP emission rate (CFR, 1992). The REP05 cycle has a
maximum speed of about 80 mph, maximum acceleration rate of about 8.5 mph/sec, and average speed of
about 51.5 mph. REP05 emissions are examined with hot start tests conducted after conclusion of the FTP
procedures described in Figure 1.  The REP05 includes two test phases: phase 1, the initial 1195 s, during
which time high speed driving modes are examined, and phase 2, the final 205 s, during which time high
acceleration rate modes  are examined. Duplicate tests are completed for all program vehicles/fuels with
criteria for a third test based on the ratio of observed emissions. A third test is required if the highest/lowest
HC emission rate ratio exceeds 1.33, the CO emission rate ratio exceeds 1.70, or the NOx emission rate ratio
exceeds 1.29 (Painter and Rutherford, 1992).

Regulated emissions (THC, CO, NOx, CO2) are sampled and analyzed using standard certification
procedures (CFR, 1992). THC emissions are reported as total non-oxygenated HC by using a procedure to
correct the THC value for FID response to oxygenated organic compounds. Organic emissions rates are also
reported as Organic Material Hydrocarbon Equivalent (OMHCE) wherein total organic carbon mass is
calculated according to procedures described in the Federal Register (CFR, 1992). In essence, the organic
                                               -17

-------
           80
       -c  60
        Q.
        E

       I  40
        a.
       w
          20
            0 "-*
                                   Federal  Test Procedure
                           500
1000        1500
    Time, sec
2000
                            500
 1000        1500
     Time, sec
2000
                           Figure 3. Transient driving schedules.

carbon mass emission rate is calculated as though each carbon atom is associated with 1.85 hydrogen atoms
(CH,.85).

Nonmethane organic gas (NMOG) emission rates are also determined.  These emissions rates are based on
summation of all organic compounds except methane, with the mass emission rates calculated using each
compounds actual molecular structure (including oxygen). Samples for exhaust detailed organic compound
analyses are collected by pumping a constant aliquot of the diluted CVS flow into Tedlar bags using a heated
(230 °F) metal bellows pump and sample line for subsequent analysis by gas chromatography. Gas
cnromatographs equipped with flame ionization detectors (FEDs) are used for detailed HC, alcohol and ether
speciation (Braddock and Crews, 1992; Zweidinger, et al, 1993; Siegl, et. al, 1993). These procedures allow
                                            18

-------
 quantitative determination of more than 300 organic compounds. Aldehyde compounds, sampled from the
 dilution tunnel through a heated (230 °F) sample line, are collected on dinitrophenyl hydrazine
 (DNPH)-coated silica gel cartridges. Individual aldehydes are collected on the cartridges as DNPH
 derivatives and subsequently extracted and analyzed by high performance liquid chromatography. This
 sampling technique and analytical method allows quantitative determination of 15 individual aldehydes
 (Tejada, 1992; Siegl, et al, 1993).
 Evaporative emissions determination

 Vehicle evaporative emissions tests are conducted in a Sealed Housing for Evaporative Determinations
 (SHED). Diurnal and hot soak evaporative emissions tests are conducted in conjunction with the FTP, as
 shown in the flowchart in Figure 1. Immediately following the transient exhaust test, the vehicle is soaked for
 I hr at 68 to 86 °F and the evaporative organics characterized as hot soak emissions. After a 6 to 36 hr soak
 at 72 °F, the vehicle temperature is cycled from 72 to 96 to 72 °F over two 24 hr periods, with the highest 24
 hr sample being characterized as diurnal emissions. At the conclusion of each evaporative test, samples are
 taken from the SHED into a 60L Tedlar bag for GC analysis of detailed HCs and oxygenated organic
 compounds using the same chromatographic procedures as used for exhaust samples. Samples are also taken
 directly from the SHED to a hot FID for THC determination. As with exhaust emissions, evaporative THC
 are reported as non-oxygenated THC by correcting the THC value for HFID response to the oxygenated
 organic compounds, and as OMHCE. G/mi equivalent emission rates are calculated to permit comparisons
 with exhaust emissions according to:

               _       .       .  .      ,  .    diurnal,  g  +  TPD( hotsoak, g )
               Evaporative emissions, g/mi =	-	—
                                                             MPD

        where:  TPD (trips per day) = 4.7187 - vehicle age * 0.058508
               MPD (miles per day) = 39.42 mi (age 1), 37.29 mi (age 2), 35.27 (age 3), etc. (U.S. EPA,
               1994).
Irradiation Chamber Studies

The photochemistry tests are completed  in an 8000 L irradiation chamber with equipment configured as
depicted in Figure 4. This chamber volume is based on two important considerations. First, a chamber of
sufficient size is required to minimize effects of dilution and to allow irradiations to be conducted over
several hours while taking a complete complement of organic and inorganic chamber samples. Second, a
relatively small surface-to-volume ratio is desired to minimize chamber wall effects.  In contrast, several
factors limit the maximum size of the chamber. The low absolute mass of ROG that can be obtained from
some test vehicles is a factor. With advanced technology vehicles, emissions are extremely low after the
catalyst becomes functional. Thus, the required masses of VOCs and NOX can be difficult to achieve for
chambers of larger size. Selection of the initial ROG/NOX ratio is also an important consideration. The
experiments are designed to allow reactivity factors to be measured for vehicle exhaust in scenarios where
hydrocarbon composition is an important variable.  As described in the Introduction section, observations are
desired for conditions where lower hydrocarbon reactivity leads to lower ozone formation. Under these
conditions radical formation rates are generally limited and are highly influenced by the hydrocarbon
composition. Thus, emission characteristics influence the conditions under which the experiments can be
carried out.
                                              19

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                           ECD FID
                                                   Carrier Row Control
                                                        Sample
                                                 Heated  Row
                                                  y?lve  Control  Pump
                                 UV Radiation Sources
Impinger for
DNPH Analysis
                                                                        300-L Teflon Bag
                                                                        for Exhaust Addition
                        Figure 4. Photochemical chamber configuration.


Hydrocarbon emissions are strongly dependent on vehicle catalyst performance.  Under the standard FTP, test
phase 1 (initial 505 s) contains ROG rich cold start emissions (emissions occurring during the initial 2 to 3 m
after the engine is started, prior to catalyst "light-off). Integrated ROG/NOX ratios during this test phase can
range from about 2 to 7, depending on the vehicle and fuel. Emissions following test phase 1 are more highly
dominated by NOX (i.e., the ratios are smaller). For advanced vehicles, even integrated phase 1 emissions can
have excessively low HC/NOX ratios. The ratio can be increased by shortening the integration period to the
first 124 s of the cold start. Urban airshed vehicle exhaust organic profiles are typically dominated by
operating conditions with high emission rates (e.g., cold start, high acceleration power enrichment, engine or
control system malfunction) with organic profiles that are reasonably represented by cold start operation.
The experiments in this series are designed to be conducted at a constant ROG/NOX ratio of 5.5.  Typically,
this experimental ratio can be achieved within ±0.5.
Facilities

Two 8000-L portable irradiation chambers are available for study of emissions photochemistry. The
primary chamber, used for the indoor experiments described in this report, is constructed of 2-mil Teflon film
fabricated by heat sealing end panels to a rectangular prism. Multiple 0.64-cm Swagelok ports, mounted
                                 in a
                                               20

-------
 Teflon plate on the bottom of the chamber, are available for sampling chamber reactants/products.  A fan is
 installed to permit active chamber mixing. Ultrazero air (Aadco, Inc., Model 737 pure air generator) is used
 for chamber flushing and reactant sample dilution. This air typically has NOX levels less than 1 ppbv and
 hydrocarbon levels less than 50 ppbC. The irradiation chamber is typically operated with a 2-3 L min"1
 dilution air flow compensating for sampling volume losses. A secondary chamber, constructed of 5-mil
 Teflon is generally used for outdoor experiments. Teflon bags having a 2-mil film thickness are typically too
 fragile for outdoor experiments (afternoon winds can easily rip the 2-mil Teflon). The chamber frames are
 attached to portable trailers, permitting both indoor and outdoor irradiations.

 The indoor irradiation system is based on 100 fluorescent bulbs of a standard 122-cm length.  A mixture of
 fluorescent bulb types is used to simulate solar spectral distribution to the extent possible. Compromising
 only the photolysis of NO3 radicals (typically formed relatively late in the reaction profile), a 300-400 nm
 radiative spectral range is provided.  Radiation in the range 300 to 350 nm is generated with UVA-340 (Q-
 Panel, Cleveland, OH) fluorescent blacklight bulbs. As illustrated in Figure 5, this bulb type matches the
 solar spectrum extremely well over this wavelength region. Radiation at wavelengths from 350 to 400 nm is
 generated with standard UV bulbs (F40-BL). The mixture of bulbs is selected to match, to the extent
possible, solar radiation between 300 and 400 nm. The major criteria for the spectral match are a photolysis
rate for NO2 similar to that which occurs at midlatitudes during the summer (i.e., 0.3  - 0.5 min"1) and an
accurate photolysis rate for carbonyl compounds relative to that for NO2. These two  criteria are fulfilled
using a 40:60 mixture of UVA-340:F40-BL. For indoor experiments, cooled air from an auxiliary air
conditioner in the laboratory is circulated in the ballast cavity, as well as between the  lights and the chamber
walls. This configuration permits the mixture temperature to be maintained between  25 and 27 °C during
irradiations.
                                     Sunlight   Fluorescent bulbs
                                           Equal Contributions
                                            to NOz Photolysis
             300
320
340           360

 Wavelength, nm
380
400
                       Figure 5.  Fluorescent lights spectral distribution.
                                               21

-------
 The secondary chamber is rolled outdoors for natural sunlight experiments (planned for the 1996 program).
 The designated chamber placement allows unencumbered illumination from approximately 8 am to 4 pm
 from mid-spring through mid-fall. For both indoor and outdoor illumination, the spectral distribution of the
 light is measured with a portable spectroradiometer (1I-COR, Inc., Model LI-1800). During experiments, the
 absolute light intensity is continuously monitored with an integrating radiometer (Eppley Laboratory, Inc.
 Newport, RI).
 Photochemical measurements

 The general experimental procedures have been previously described (Kleindienst et al., 1992; 1994; 1995).
 Tests to evaluate chamber performance, completed before initiation of the study, include determination of the
 photolysis rate of the irradiation source and determination of chamber wall radical source and reactivity.
 Prior to experimental runs with exhaust, the chamber is flushed with ultrazero air for 24-48 h. Background
 samples are taken to verify negligible levels of hydrocarbons and carbonyls prior to reactant addition.

 The exhaust mixture is collected from the dilution tunnel into intermediate Teflon bags (each 300 L in
 volume) with heated metal bellows pumps. Line connections use heated Teflon tubing. After collection, the
 integrated ROG and NOX are analyzed and injected into the irradiation chamber using a metal bellows pump.
 The actual injection volume is generally dependent on the concentrations of NOX in  the sample. Exhaust is
 injected into the chamber to bring the initial chamber NOX concentration to a target  value of 400 ppbv. The
 sample transfer procedure is quality assured by contrasting CVS exhaust compositions with compositions
 observed in the initial irradiation chamber mixture.

 Experiments are conducted at an initial ROG/NOX ratio of 5.5, accentuating differences in HC reactivity.
 Many vehicles achieve this ratio in the 124-s sample, mitigating requirements for additional hydrocarbon
 from a surrogate source.  In cases where additional hydrocarbon is required to meet  ROG/NOX requirements,
 an exhaust surrogate (based on fuel and significant combustion products) is used. If the initial ROG/NOX
 ratio is higher than 5.5, NO is added.

 Once the reactant mixture is added to the chamber, initial samples (i.e., time zero irradiation samples and
 parameters) are taken and the irradiation is initiated. Physical parameters including  temperature and radiation
 intensity, and  inorganic compound concentrations (i.e., NO, NOX, O3), are monitored continuously during the
 irradiation.  Samples for peroxyacyl nitrates are taken at 0.5-h intervals. Detailed ROG samples and carbonyl
 samples are taken at 2-h intervals.  Nitric acid samples are obtained initially and at the end of the irradiation.
 Gas-phase species are measured using standard analytical techniques. Most samples are collected from a
 200-ml Teflon manifold that is  connected to the chamber by a Teflon sampling tube. The sampling line is
 inserted 45 cm above the  chamber floor to ensure that a well-mixed and representative gas sample is
 obtained. Nitric oxide (NO), total NOX, and ozone are measured with continuous monitors using previously
 described techniques (Kleindienst et aL, 1992; 1994; 1995). Temperature and relative humidity (RH) are
 measured with a Omega digital Thermo-Hydrometer (Model RH411). The temperature-humidity sensor is
placed in an insulated Teflon tube that is located in-line with samples taken from the 200-ml manifold. Air
 samples drawn past the temperature and RH sensor are in close proximity to the irradiation chamber, but
 shielded from the UV lights.  This approach permits the air temperature of the chamber samples to be
 measured while avoiding  radiative heating from UV bulbs or sunlight.

Organic precursor and reaction  product concentrations are determined as a function  of irradiation time.
Speciated hydrocarbons are measured by GC with detection by flame ionization (FID), electron capture
(BCD), or mass spectrometry (MS). Chamber samples for detailed nonmethane hydrocarbon (ROG) analysis


                                              22

-------
are cryogenically condensed to provide adequate detector sensitivity. Sample volumes are typically 100 ml
and are analyzed using a methyl silicone column (Restek Corp. RTX1,60 m x 0.32 mm, l-/^m film thickness)
connected serially to a Carbowax column (Restek Corp. Stabilwax, 30 m x 0.32 mm, 0.5-^m film thickness).
This approach substantially improves the peak shape of polar compounds produced during the irradiation and
permits separation of methanol from C4 hydrocarbons. Methyl nitrite is also measured by GC using an open-
loop and a 2-m, 0.75-mm HayeSep S micropacked column with BCD detection.

Aldehydes and ketones are sampled by bubbling the effluent through a solution containing 2,4-
dinitrophenylhydrazine (DNPH) in acidified acetonitrile. The derivatization reactions produce carbonyl
hydrazones which are analyzed by HPLC (Milton Roy, Model CM4000). A Zorbax ODS-1 column
analytical column is used. Hydrazone aldehyde derivatives are detected by UV absorption at 360 nm. A
ternary gradient, composed of acetonitrile, methanol and water, is used to provide adequate separation of both
low and intermediate molecular weight aldehydes.

Peroxyacetyl nitrate (PAN) is measured by GC/ECD.  The trifluoropropyl methyl silicone (Restek RTX-200;
30 m x 0.53 mm, l-//m film thickness) column used for analysis is of moderate polarity, giving an elution
order similar to those obtained with a standard Carbowax column.  The  column, operated at room
temperature, provides baseline separation of PAN and peroxypropionyl nitrate (PPN) and mitigates moisture
problems. The carrier gas is ultrahigh purity hydrogen. Detection is provided by a 63Ni ECD with argon/5%
methane (P5) used as the make-up gas. These conditions provide excellent separation with minimum
residence time.  The detection limit for PAN is 2 fmol (50 pptv).

The total irradiation time is typically 12  h,  or the time required to reach  a peak in ozone concentration. A 12
h maximum irradiation time mitigates dilution effects. More importantly, under these conditions the
integrated light intensity at 300-400 nm  (i.e., the photolyzing wavelengths for carbonyls and NO2) is similar
to that of a summer day at midlatitudes (ca. 30-50°).  Peak ozone concentration may not be observed during a
12-h irradiation with the low exhaust reactivities characteristic of some fuels (e.g., CNG).
                                              23

-------
                          Results and Discussion

Emissions Results

Emission rates are determined for each vehicle and fuel technology using both FTP and REP05 transient
driving simulations. Table 3 provides exhaust NMOG, CO, and NOX emission rates (g/mi) for each vehicle,
fuel, and driving schedule. REP05 results include REP05-1, the first 1195 sec (see Figure 3) during which
high speed driving modes occur, REP05-2, the final 205 sec during which high acceleration driving modes
occur, and REP05-C, the composite of these periods. For all vehicles except the Dodge Caravan, the CO
emission rates are more than an order of magnitude higher for the REP05-2 (high acceleration) driving
schedule than the FTP schedule. Elevated CO emission rates are associated with high acceleration rates
resulting from power enrichment; however, the Dodge Caravan horsepower/weight ratio apparently is
adequate to avoid power enrichment at REP05-2 acceleration rates. NOX emissions are also generally
elevated by high acceleration rate driving conditions. Contrasting the FTP exhaust emission performance of
the various vehicles with different fuels: all emission rates are lower for the Dodge Caravan  with CNG fuel
Table 3. Regulated Emissions.

R FG
FTP
R E P 05-1
R EP 05-2
R E P 05-C
CNG
FTP
R E P 05-1
R E P 05-2
R E P 05-C

R FG
FTP
R E P 05-1
R E P 05-2
R E P05-C
£85
FTP
R E P 05-1
R EP05-2
R E P 05-C
Dodge C
NMOG, g/mi
0.1 54
0.059
0.08 1
0.062
NMOG, g/m i
0.006
0.005
0.007
0.005
L u m in a
NMOG, g/m i
0.140
0.078
1.138
0.233
NMOG, g/m i
0.244
0.030
0.192
0.053
a ra va n
C O , g/m i
1 .704
1 .380
3.127
1 .636
CO, g/mi
0.538
0.170
0.930
0.281
V F V
CO, g/mi
1 .969
3.820
85.060
1 5.71 6
CO, g/mi
3.190
3.285
58.8 1 5
1 1 .4 1 6

N O x , g/mi
0.294
0.140
0.457
0.186
N O x , g/mi
0 .0 1 9
0.090
0.320
0.1 24

N O x , g/mi
0.270
0.175
0.130
0.168
N O x , g/mi
0.177
0 .060
0 .650
0.146
                                            24

-------
Table 3 (con't). Regulated Emissions.
R FG
FTP
R EP05-1
REP05-2
R EP05-C
M 85
FTP
REP05-1
R EP05-2
R EP05-C
s pint
N M OG , g/m i
0.151
0.058
0.584
0.135
N MOG. g/mi
0.284
0.042
0.344
0.086
FFV
CO, g/mi
3.358
2.550
33.830
7.1 30
CO, g/m i
5.137
3.825
63.365
12.543
N 0 x, g/m i
0.153
0.195
1 .495
0.385
N 0 x . g/m i
0.1 73
0.155
0.565
0.21 5
                                         Taurus FFV

             RFG           NMOG,g/mi         CO.g/mi          NOx.g/mi
FTP
REP05-1
R EP05-2
R EP05-C
0.1 16
0.098
0.716
0.188
1 .440
2.930
49.070
9.686
0.176
0.075
0.630
0.1 56
             M85           NMOG.g/mi         C0,g/mi          NOx.g/mi

             FTP               0.304               2.480               0.243
          REP05-1             0.086               1.700               0.060
          REP05-2             0.203               36.695               0.590
          REP05-C             0.103               6.824               0.138
than with RFG fuel; NMOG and CO emission rates are higher for the Lumina with E85 fuel than with RFG
fuel, but NOX rates are lower; all emission rates are higher for the Spirit with M85 fuel than with RFG fuel;
and all emission rates are higher for the Taurus with M85 fuel than with RFG fuel. It is interesting to note
that the Dodge Caravan emission rates with CNG fuel are well below the California Ultra Low Emission
Vehicle (ULEV) standards of 0.040 g/mi NMOG, 1.7 g/mi CO, and 0.2 g/mi NOX.
Observations with FTP Driving Simulations

Table 4 provides comparisons of FTP exhaust and evaporative NMOG and OMHCE emission rates for each
vehicle and fuel. NMOG includes summation of all organic emissions, exclusive of methane, with mass
calculations based on each compounds actual molecular structure (includes oxygen mass for oxygenated
compounds). OMHCE includes summation of all organic compounds with mass calculations based on the
assumption that each carbon atom is associated with 1.85 hydrogen atoms (i.e., CH[ 85). This practice
provides for uniform application of historical Federal THC standards to all fuels (i.e., the hydrocarbon
equivalent of gasoline emission rates when fuel contains oxygen or has a significantly different H/C ratio than
gasoline).  The relationship of OMHCE emission rates to NMOG emissions rates depends on the
composition of the emissions. Excluding the CNG Caravan with no evaporative emissions, evaporative
emissions  accounted for 34% to 84% of vehicle total NMOG emissions. The high evaporative emission
rates observed with the Taurus resulted from a deteriorated rubber hose between the fill cap and the fuel tank.
                                              25

-------
            Table 4. FTP Exhaust and Evaporative NMOG and OMHCE Emissions.

                      Exhaust                 Evap.                     Total
                 NMOG,   OMHCE,    NMOG,     OMHCE,      NMOG,    OMHCE,
                  g/mi        g/mi        g/mi        g/mi         g/mi         g/mi
Caravan,
RFG
Caravan,
CNG
Taurus,
RFG
Taurus,
M85
Spirit,
RFG
Spirit,
M85
Lumina,
RFG
Lumina,
E85
0.154
0.006
0.116
0.304
0.151
0.284
0.140
0.244
0.198
0.094
0.146
0.191
0.201
0.171
0.176
0.299 "
0.117
0.000
0.613
0.355
0.161
0.190
0.182
0.126
0.128
0.000
0.647
0.355
0.192
0.192
0.200
0.105
0.271
0.006
0.729
0.659
0.312
0.474
0.322
0.370
0.326
0.094
0.793
0.546
0.393
0.363
0.376
0.404
 This hose permeated organic vapors. With this vehicle, evaporative NMOG emissions are reduced about
42% with M85 fuel compared to RFG fuel. Generally, evaporative emission rates are lower with the
alternative fuel (CNG, M85, E85) than with RFG fuel (excepting the Spirit). In each case, exhaust NMOG
emission rates are higher with the alcohol fuels than with RFG fuel.

The ozone forming potential of emissions depends upon both emission rates and composition.  Vehicle
emissions ozone potential can be estimated algebraically by associating Carter reactivity with g/mi emissions
rates.  Figure 6 provides mg/mi ozone potential estimates for each vehicle-fuel pair examined in this program.
The lowest ozone potential is clearly associated with the Caravan-CNG technology. The data also provide an
overview of the relative contributions of exhaust (NMOG and CO) and evaporative (NMOG) emissions.
Resulting primarily from the lower emission rate, the Taurus evaporative ozone potential is reduced
significantly with M85 fuel compared to RFG.  Appendix B provides an overview of the relative
contributions of alkane, alkene, aromatic, alkyne, alcohol/ether, and aldehyde/ketone organic compounds, and
CO to exhaust and evaporative ozone potential for each vehicle and fuel tested. It is interesting to note that
with the 85% alcohol fuels (M85, E85), 40% to 63% of the emissions (exhaust plus evaporative) ozone
potential comes from alkane, alkene, and aromatic hydrocarbons. An additional 12% to 29% of the ozone
potential with these fuels comes from exhaust CO emissions.
                                             26

-------
           2,000
                          Figure 6. FTP ozone potential (Carter MIR)

As discussed in Experimental, the initial 124 s of the FTP cold-start test is used to provide samples  for
irradiation chamber examination of exhaust atmospheric chemistry. Figure 7 illustrates the similarity of the
124 s NMOG Carter MIR specific reactivities (mg ozone per mg NMOG) for each fuel to that of the
weighted FTP exhaust. The 124s reactivities are slightly higher than the weighted FTP values. Evaporative
      CD
                                                          RFG
                                                          CNG
                                                          ESS
                                                          MBS
Exh-124       Exh-WTD
                                                         Evap
                    Figure 7. FTP NMOG specific reactivity (Carter MIR)
                                             27

-------
          TableS. FTP NMOG MR
           Specific Reactivity Ratios
Ratio       wtd Exhaust  Wtd Evaporative
CNG/RFG      0.87
                                NA
E85/RFG
M85/RFG
0.70
0.36
0.60
0.69
                                                     emissions specific reactivities are also
                                                     provided for comparison. RFG and E85
                                                     evaporative NMOG emissions reactivity is
                                                     lower than exhaust, and M85 evaporative
                                                     NMOG emissions reactivity is higher than the
                                                     exhaust.  Table 5 provides alternative fuel /
                                                     RFG fuel MIR specific reactivity ratios for
                                                     weighted FTP exhaust and evaporative
                                                     NMOG emissions. These values are similar
                                                     to California RAFs, except that the alternative
                                                     fuel reactivities are ratiod to RFG reactivities,
                                                     rather than to baseline unleaded gasoline. The
                                                     data indicate that most of the CNG exhaust
                                                     NMOG ozone potential (ozone g/mi) benefit
                                                     results from reduced emission rates. It also
suggests that M85 exhaust emission rates can exceed RFG emission rates by a factor of 2.8 with similar
NMOG ozone potential. For example, the Taurus NMOG exhaust emission rates are 0.116 g/mi with RFG
and 0.304 g/mi with M85; MIR NMOG ozone potential is about 0.38 g/mi with both fuels. Appendix C
provides detailed exhaust and evaporative emissions profiles with Carter MIR and MOR ozone potentials and
specific reactivities for each vehicle-fuel pair and driving simulation examined.

Recent California data suggest that the RAF (referenced to baseline industry average unleaded gasoline) for
RFG = 0.94, E85 = 0.63, M85 = 0.37, and CNG = 0.43 (CARS, 1995).  Reported RAF's for CNG exhaust
have varied from low values near 0.18 to a high value in this study of about 0.87. Examination of emissions
characteristics suggests that as CNG NMOG emissions rates decrease, associated RAF's increase. This
results from an increased contribution of uncombusted fuel (with very low MIR reactivity) to emitted NMOG
as the emission rate increases. Figure 8 is a plot of several observed exhaust MIR specific reactivities versus
       3.5
   o
   2      3
5s   2.5
o
O)
.£?      2
1
S   1.5

3
o      7
Q>      '

I   0.5

        O
                 RAF = O.87
                    RAF = O.S8
                    O.1      O.2     O.3     O.4      O.5     O.6      O.7
                                     NMOG. g/rnl

Figure 8.  CNG exhaust MIR Specific Reactivity versus NMOG emission rate (RAF values
assume base gasoline specific reactivity = 3.46)
                                         28

-------
 NMOG emission rates. The California CNG RAF of 0.43 would be consistent with a NMOG emission rate
 near 0.125 g/mi.

 Figure 9 provides toxic compound (i.e., formaldehyde, acetaldehyde, benzene, and 1,3-butadiene) emission
 rates foreach vehicle-fuel pair tested. The data are ordered from top to bottom in the tables as the compounds
 are illustrated top to bottom in the bar charts. Formaldehyde, acetaldehyde, and  1,3-butadiene are
 combustion products, and thus not associated with evaporative emissions.  With  RFG fuel, benzene is the
 most abundant toxic emission, followed by formaldehyde. Generally, exhaust benzene emission rates exceed
 evaporative rates. The Taurus is an exception due to the previously discussed evaporative control system
            30
            25
         I 20
         I  10
         LLI
             5
                    Reformulated
                      Gasoline

FbrmakJ.
Acetak).
Butadiene
Benz-exh
Benz-evap
Caravan
2,9
0.9
0.5
5.0
1.8
Taurus
2.5
0.9
0.4
3.7
7.0
Spirit
1.8
0.4
0.4
5.9
29
Lurrina
25
0.5
0.1
4.8
3.0
Alternative
   Fuels

For ma Id.
Acetald.
Butadiene
Benz-exh
Benz-evap
Caravan
0.7
0.0
0.0
0.1
0.0
Taurus
14.9
0.2
0.0
1.8
25
Spirit
14.5
0.2
0.0
1.5
1.7
Lumina
4.0
18.8
0.1
24
0.6
                           Figure 9. FTP toxic compound emissions

malfunction (i.e., vapors permeating rubber hose between fill cap and fuel tank).  For the alternative fuels,
formaldehyde dominates with CNG and M85, and acetaldehyde dominates with E85. Methyl tertiary butyl
ether (MTBE) emissions are of interest with RFG fuel.  Figure 10 provides MTBE exhaust and evaporative
emission rates for the vehicles examined in this program.  Evaporative emission rates exceed exhaust rates
for all vehicles, with the Taurus data again excessively high resulting from the malfunction fuel hose
condition.
                                              29

-------
       E
       o>
       E
       UJ
       m
80


60


40


20
Evaporative
Exhaust
                  Caravan Taurus    Spirit   Lumina
                               Figure 10. FTP MTBE emissions


Observations with REP05 Driving Simulations

As previously discussed, the REP05 driving simulation differs from the FTP simulation in that it does not
include cold start operation, but does include higher speeds and higher acceleration rates. The driving
schedule is structured to permit examination of high speed (REP05-1) and high acceleration rate (REP05-2)
modes separately. Figure 11 provides an overview of REP05-1 and REP05-2 Carter MIR ozone potentials
that can be compared to Figure 6 FTP simulation data. Generally, ozone potential is less under high speed
operation, probably resulting from higher catalyst temperatures and less deviation from stoichiometric
combustion (more efficient catalyst organic oxidation), and greater under high acceleration rate operation,
probably resulting from power enrichment with an open-loop fuel-rich shift from stoichiometric combustion
(less efficient catalyst organic oxidation). The Taurus and Lumina both exhibit an exhaust ozone potential
benefit from use of alcohol fuel.  This is not observed using the FTP simulation, likely because of the impact
of FTP cold start operation.

Figure 12 presents REP05-1 and  REP05-2 Carter MIR NMOG specific reactivity data.  There are notable
differences from the FTP data. Generally,  REP05-2 exhaust reactivity is greater than FTP exhaust reactivity
with alcohol fuels. A reversal of driving simulation specific reactivity fuel sensitivity is observed with the
Lumina. FTP specific reactivity is lower with E85 fuel than with RFG fuel, whereas it is higher with E85 fuel
than with RFG fuel with the REP05 simulation. Examining the Lumina compositional data in Appendix C,
with the FTP simulation, alkenes constitute about 40% of exhaust ozone potential with RFG fuel and 27%
with E85 fuel; and with the REP05-2 simulation, alkenes constitute about 29% of exhaust ozone potential
with RFG fuel and 74% with E85 fuel. The Lumina E85 REP05-2 ozone potential benefit (compared to
RFG) noted in Figure 11 results from reduced emission rates, reductions that more than offset the increased
E85 specific reactivity.
                                             30

-------
                    REP05-1
     REP05-2
     500


  |  400

  I
  15  300

  I
  £  200
  
        /

                      A
                                               *
  -
/
                  Figure 12. REP05 NMOG specific reactivity (Carter MIR)

Figure 13 presents REP05 toxic emissions characteristics. High speed (REP05-1) emissions are not
dramatically different than FTP emissions, except for a higher Lumina RFG benzene emission rate, and a
lower Lumina E85 acetaldehyde emission rate. However, dramatic differences are observed for the high
acceleration rate (REP05-2) simulation. Benzene emission rates are highly elevated above FTP benzene
emission rates with liquid fuels. FTP rates ranged from 1.5 to 5.9 mg/mi, REP05-2 rates ranged from 18.9 to
162.9 mg/mi.
                                            31

-------
             Reformulate Gasoline
                                                     Alternative Fuels
       25
    E  20
    t»
    E

    *  15
a.   tt
UJ   c
Of   o
    
-------
              Table 6. Fuel economy

  Vehicle, Fuel        MPG           BTU/mi
Caravan, RFG
Caravan, CNG
Lumina, RFG
Lumina, E85
Taurus, RFG
Taurus, M85
Spirit, RFG
Spirit, M85
17.1
17.7
18.2
14.1
19.9
12.5
22.5
13.5
6351
6269
6167
5857
5630
5345
4975
4948
 Fuel Economy

 Fuel economy is determined for the FTP driving
 simulation with each vehicle and fuel both in terms
 of miles traveled per gallon of fuel consumed
 (mpg) and British Thermal Units of energy
 consumed per mile traveled (BTU/mi). CNG mpg
 estimates are based on a gasoline equivalent
 relationship defined in the Federal Register (FR,
 1994).  A 100 std ft3 volume of CNG is the energy
 equivalent of 0.823 gal of gasoline. The test
 program CNG had 940 BTU/ft3. Results are
 reported in Table 6.  Small energy efficiency
 improvements are observed for all vehicles when
 using alternative fuels, with the Lumina and
Taurus both indicating about 5% gains with E85
and M85, respectively, compared to RFG. The
reduction of mpg fuel economies with alcohol fuels
compared to RFG fuel are consistent with fuel
relative energy contents (RFG fuel 112,238.6
BTU/gal, E85 fuel 82,914.2 BTU/gal, and M85
fuel 66,744.8 BTU/gal) and efficiencies.
Irradiation Chamber Assessments
A series of experiments are described examining differences in the atmospheric photochemistry of motor
vehicle emissions with alternative fuels using indoor photochemical chamber irradiation of the exhaust. As
previously discussed, cold start exhaust is used to maximize the ROG/NOX concentration ratio. A number of
reactivity parameters can be determined from the chamber data and used to characterize differences in the
exhaust chemistry with different fuel formulations.  Ideally, the reactivity measures are related to the
propensity of the ROG/NOX mixtures to form ozone.

Chamber Qualifications

The program irradiation chamber light spectral distribution and NO2 photolysis rate was previously
characterized and reported (Kleindienst, 1994). Before initiating 1995 tests, a series of CH4/NOX and
CO/NOX irradiations were completed to assess the significance of the chamber walls as a radical source,
propylene/NOx runs were completed to assess ozone losses to the walls, and protocols for transfer of vehicle
exhaust to the chamber were evaluated to assure insignificant losses. A series of tests were completed to
examine transfer losses of compounds of interest between the vehicle tailpipe and the irradiation chamber.
Known concentrations of individual compounds (propane, cyclohexane, formaldehyde, and methanol) and
mixtures (gasoline and auto exhaust) were injected into the sample transfer system with losses monitored to
the chamber (Stump, et al, 1995). No losses were observed in the sampling system with transfer lines  and
pumps heated to 230 °F.
                                             33

-------
Experimental Observations

Chamber tests completed to examine the ozone potential of exhaust and/or surrogate mixtures are described
in Table 7. Surrogate additions were typically necessary with RFG and CNG fuels to achieve target
ROG/NOX ratios (~ 5.5).  As previously discussed, ROG surrogates were based on vaporized liquid fuels
with ethylene, propylene, and sometimes formaldehyde or acetaldehyde added; and a 7 component organic
mixture for CNG fuel. Final surrogate mixture compositions are provided in Table 8.
Table 7. Irradiation chamber run summary.
Run
No.
IR51
IR52
IR53
IR54
IR56
IR58
IR59
IR60
IR61
IR62
IR64
IR65
IR66
IR67
IR68
IR69
IR70
IR71
IR72
IR74
IR75
Fuel/Vehicle
RFG/Caravan
RFG/Caravan
RFG
RFG/Taurus
M85
M85 (with HCHO)
M85/Taurus
M85/Taurus
M85/Taurus
RFG/Spirit
RFC/Spirit
M85/Spirit
M85/Spirit
M85 (with HCHO
and methyl nitrite)
RFG/Lumina
RFG/Lumina
E85/Lumina
E85/Lumina
RFG/Lumina
CNG/Caravan
CNG/Caravan
Total ROG
(ppmC)
2.001
2.511
2.206
2.210
2.553
2.354
1.474
2.125
2.450
2.334
2.210
1.599
1.860
2.360
2.340
2.520
2.210
2.060
2.240
2.540
2.700
% Surrogate
ROG
61.8
57.5
100.0
57.2
100.0
100.0



27.4
49.5


100.0
42.1
34.0


14.7
93.8
94.7
NOX
(ppmv)
0.350
0.424
0.401
0.401
0.394
0.395
0.314
0.394
0.409
0.413
0.410
0.298
0.367
0.398
0.386
0.398
0.396
0.394
0.398
0.419
0.469
ROG/NOX
ratio
5.720
5.922
5.501
5.511
6.480
5.960
4.694
5.393
5.990
5.651
5.390
5.366
5.068
5.930
6.062
6.332
5.581
5.228
5.628
6.062
5.757
                                             34

-------
Run
No.
IR76
IR77A
IR78
Fuel/Vehicle
RFG
E85
CNG
Total ROG
(ppmC)
2.140
2.190
2.110
% Surrogate
ROG
100.0
100.0
100.0
NOX
(ppmv)
0.381
0.409
0.385
ROG/NOX
ratio
5.617
5.355
5.481
Table 8.  Surrogate compositions.
Organic
Group
Alkanes
Alkenes
Aromatics
Oxygenates
Unknowns
RFG
ppmC%
49.1
15.7
27
8.1
0.1
M85
ppmC%
18
3.3
7
71.7
0
E85
ppmC%
12.5
9.4
5.4
72.6
0
CNG
ppmC %
71.1
23.1
0
5.8
0
The photochemistry of motor vehicle exhaust emissions associated with combustion of alternative fuel
formulations is presented by describing the initial composition of the exhaust and/or surrogate mixture in the
chamber, the photooxidation products after 12 h of irradiation, and the observed reactivity parameters for
each vehicle-fuel pair examined. This data is provided in Appendix D for the runs described in Table 7.
Time resolved (12 h) profiles of key inorganic (NO, NO2,03) and organic (PAN and selected carbonyls)
species are provided in Appendices E and F, respectively.

The exhaust associated with combustion of RFG fuel was studied with a conventional fuel Dodge Caravan (2
tests), and a flexible-fuel Ford Taurus (1  test), Dodge Spirit (2 tests), and a Chevrolet Lumina (3 tests).
Ozone concentrations at 12 h ranged from 471 to 664 ppbv (average 582, n = 8). As indicated in the
Appendix E plots, clear ozone maxima were not observed during the 12 h irradiations. PAN concentrations
after 12 h RFG exhaust irradiation ranged from 16.6 to 31.1 ppbv  (average 20.4, n = 8); formaldehyde from
36.4 to 94.4 ppbv (average 65.1, n = 8); and acetaldehyde from 13.8 to  18.5 ppbv (average 16.5, n = 8).
Exhaust associated with combustion of M85 fuel was studied with a flexible-fuel Ford Taurus (4 tests), and
a flexible fuel Dodge Spirit (2 tests). Ozone concentrations at  12 h ranged from 166 to 369 ppbv (average
305 , n = 5). PAN ranged from 1.0 to 3.2 ppbv (average 2.2, n = 5 ); formaldehyde from 41 to  100 ppbv
(average 67.5, n = 5 ); and acetaldehyde from 3.9 to 5.9 ppbv (average 5.1, n = 5). Exhaust associated with
combustion of E85 fuel was studied with a flexible-fuel Chevrolet Lumina (2 tests). Ozone concentrations at
12 h ranged from 535 to 562 ppbv (average 549, n = 2). PAN concentrations ranged from 21.7 to 27.3
ppbv (average 24.5, n = 2); formaldehyde from 85 to 125 ppbv (average 105, n = 2) and acetaldehyde ranged
from 67 to 70 ppbv (average 68.3, n = 2). Exhaust associated with combustion of CNG fuel was studied
with a dedicated-fuel Dodge Caravan (2 tests). Ozone concentrations at 12 h ranged from 112 to 137 ppbv


                                               35

-------
 (average 125, n = 2).  PAN concentrations ranged from 1.1 to 1.3 ppbv (average 1.2, n = 2); formaldehyde
 from 91 to 104 ppbv (average 97.5, n = 2); and acetaldehyde from 10.7 to 11.0 (average 10.9, n = 2).

 Table 9 summarizes observed reactivity parameters for each fuel. The Carter data is based on the first 124 s
 of the cold start FTP (sample used in chamber irradiations). The exhaust relative ozone potential indicated
 by Carter Specific Reactivity for total NMOG, CO, and CH4 correlates very well with observed 12 h ozone
 concentrations.  RFG and E85 vehicle exhaust ozone potentials (per unit NMOG, CO, and CH4 mass
 emissions) were similar under the study test conditions, M85 ozone potential was about 1/2 that of RFG, and
 CNG ozone potential about 1/5 that of RFG.
 Table 9.  Ozone reactivity parameter summary.
Fuel Carter NMOG Carter NMOG, CO, Ratio fuel/RFG 12 h ozone cone.,. Ratio fuel/RFG
Spec. React. CH4 Spec. React. ppbv
RFG
E85
M85
CNG
Fuel
RFG
E85
M85
CNG
3.74
2.29
1.05
3.47
-dNO/dt
max.,
ppbv/min
2.16
2.26
2.68(1.56) '
1.08
0.455
0.404
0.207
0.093
dNO2/dt
max.,
ppbv/min
1.82
1.87
2.09
0.77
1.00
0.89
0.45
0.20
dO3/dt
max.,
ppbv/min
1.23
1.18
0.64
0.64
582
549
305
125
NO/NO2 NO/O3
crossover, crossover,
min min
90.3 182.8
98.5 213.0
72.8 219.6
262.0 503.5
1.00
0.94
0.52
0.21
NO2
max., min
184.1
226.5
229.2
496.5
 With M85 -dNO/dt is not linear with time. The slope is notably lower at NO/NO2 crossover than the max.
value (see D-l 1 through D-15).
Plots of the loss of NO (rf[NO]/dt) at the beginning of the irradiation for RFG, CNG, and E85 emissions
show initially a short period (e.g., <0.5 h) of little conversion to NO2, follow by a period of linear rapid
conversion. This period of a rapid linear conversion provides the maximum observed d[NO]/dt reactivity
factor.  As NO is depleted to less than 25% of its initial value, the rate of conversion of NO to NO2 decreases
substantially as seen in a typical run for RFG exhaust. The initial period represents a time required to
initially generate radicals in the system (frequently through chamber wall processes). As formaldehyde and
other carbonyls are formed, their high reactivity and potential for generating radicals directly through
photolysis, leads to the increased rate of NO conversion represented by the maximum in the reactivity factor,
                                              36

-------
 If' we consider the irradiation of methanol exhaust, however, we see that the system is most reactive at the
 beginning of the irradiation.  Part of the reason for this high initial conversion of NO to NO2, is the presence
 of high levels of HCHO in the exhaust. This is demonstrated from the results of the M85 exhaust surrogate
 experiments (i.e., IR56, IR58, and IR67). The formaldehyde concentration of the surrogate was intentionally
 varied in the three runs with no HCHO added in IR56; 127 ppbv in IR58; and 20 ppbv in IR67. Most of the
 other initial variables were held constant. Both runs with added HCHO showed negative curvature in a
 consistent fashion indicating that the presence of HCHO is at least partially due to the fast initial rate.
 However, the magnitude of the effect particularly in IR58 (where HCHO was 127 ppbv) was not nearly as
 dramatic as that observed in IR60, IR61, and IR66.  This suggests the possible presence of a second reactive
 component which is rapidly depleted during the irradiation. It is the depletion of a radical generating
 constituent (via photolysis) that can lead to curvature in the loss of NO with time seen in the plots of
 irradiated M85 exhaust.  An obvious candidate for this undetected compound is methyl nitrite.

 The formation of methyl nitrite in M85 exhaust is possible given the relatively high concentrations of
 methanol and NO during the period immediately following combustion. In an attempt to examine the effect
 of methyl nitrite in exhaust mixtures, 3.7 umol of methyl nitrite was injected into the initial surrogate mixture
 in run i R67, giving an equivalent initial chamber concentration of 10 ppbv. While the initial formaldehyde
 concentration was somewhat lower than that in M85 exhaust runs of IR60, IR61, and IR66, the IR67
 irradiation did not show the initial dramatic conversion of NO to NO2 observed in the M85 exhaust runs.
 Thus, it is unclear what compound(s) gives rise to the rapid loss of NO with time in irradiations of M85
 exhaust.

 The following exhaust reactivity  rank ordering results from each of the examined reactivity parameters:

       Carter MIR NMOG
         Spec. React.                        RFG ~ CNG > E85 > M85
       Carter MIR NMOG, CO,
         CH4 Spec. React.                   RFG ~ E85 > M85 > CNG

       12 h ozone cone., ppbv                RFG - E85 > M85 > CNG
       -dNO/dt (max.), ppbv/min             M85 > E85 ~ RFG > CNG
       -dNO/dt (CrOv), ppbv/min            RFG - E85 > M85 > CNG
       dNO2/dt, ppbv/min                   M85 > E85 - RFG > CNG
       dO3/dt, ppbv/min                     RFG - E85 > M85 - CNG
       NO/NO2 CrOv, min                   M85 > RFG -E85 » CNG
       NO/O3 CrOv, min                    RFG > E85 - M85 » CNG
       NO2max.,min                       RFG > E85 ~ M85 » CNG

Actual ozone concentrations observed after 12 h irradiations suggest that RFG exhaust reactivity ~ E85
exhaust reactivity > M85 exhaust reactivity > CNG exhaust reactivity; Carter MIR NMOG, CO, CH4
exhaust specific reactivity and the slope -dNO/dt at NO/NO2 crossover agree with this rank ordering.

Table 10 summarizes some of the toxic compound concentrations observed in the chamber after 12 h exhaust
irradiations. The PAN concentrations were substantially lower with M85 (2.2 ppbv) and CNG (1.2 ppbv)
fuels than with RFG (20.4 ppbv)  and E85 (24.5) fuels, and acetaldehyde concentrations substantially higher
with E85 (68.3 ppbv) fuel than RFG (16.5 ppbv), M85 (5.1 ppbv), or CNG (10.9 ppbv) fuels.
Formaldehyde concentrations were higher with E85 (105 ppbv) and CNG (97.5 ppbv) fuels than with RFG
(65.1 ppbv) and M85 (67.5) fuels. Examining the time resolved chamber concentration profiles in Appendix
F, formaldehyde concentrations increase during irradiation of RFG, E85 and CNG exhaust; and the
                                             37

-------
 Table 10. Toxic compound concentrations after 12 h exhaust irradiations.

  Fuel                          PAN, ppbv             HCHO.ppbv           CH3CHO,ppbv
RFG
E85
M85
CNG
20.4
24.5
2.2
1.2
65.1
105.0
67.5
97.5
16.5
68.3
5.1
10.9
formaldehyde profile is relatively flat during irradiation of M85 exhaust.  Photochemical oxidation of
ethylene (~ 26% of NMHC emissions with both E85 and CNG fuels) and acetaldehyde (with E85 fuel) are
principally responsible for the photochemical formaldehyde with E85 and CNG fuels. PAN is also a
photochemical product of acetaldehyde with E85 fuel.

Chamber studies of the ROG surrogate mixtures for RFG, M85, E85, and CNG fuels were also completed.
As previously discussed, the surrogates were prepared by vaporizing the liquid fuels and adding ethylene,
propylene, and formaldehyde or acetaldehyde. M85 fuel was tested with no added formaldehyde, 20 ppbv
added formaldehyde, and 127 ppbv added formaldehyde.  The E85 fuel was tested with 39 ppbv added
acetaldehyde. The CNG ROG surrogate was prepared by blending ethane (39.4 ppmC %), ethylene (20.0
ppmC %), propane (24.7 ppmC %), propylene (3.0 ppmC %), isobutane (3.1 ppmC %), n-butane (3.9 ppmC
%), and formaldehyde (5.8 ppmC % ).

Contrasting the fuel surrogate irradiation 12 h ozone concentrations and -dNO/dt (CrOv) reactivity
parameters with those observed during the associated exhaust irradiations suggests that the fuel surrogate
ROG may not have been as reactive as the exhaust ROG.  The combustion product organics may not be
adequately represented by the surrogates.  However, the observed differences in 12 h ozone  concentrations
are not suggested by differences in Carter MIR specific reactivities for the exhaust and associated surrogates.
(e.g., RFG surrogate MIR specific reactivity = 3.80,124 exhaust = 3.74). Differences in initial chamber
water concentrations may also have contributed to some of the observed differences. The surrogate chamber
tests were conducted without water added to simulate that associated with diluted auto exhaust. This could
have reduced OH radical concentrations (resulting from O3 + hv - O(!D) + O2, O(*D) +H2O-» 2OH) after
chamber NO is depleted. In this latter case, the actual exhaust runs would not have been compromised since
the surrogate exhaust ROG was added to actual exhaust, including water vapor. The surrogate uncertainties
will be further studied during the 1996 program.
             Comparison  of Results  with Other Studies


Because of the limited number of vehicle/fuel pairs examined in the reported study, it is uncertain if the
results are representative of the technologies. Table 11 provides comparisons of the weighted FTP regulated
exhaust emissions observed in this study with those observed in several recent studies involving similar fuels.
Care must be taken when comparing specific results from different studies because of potential vehicle-to-
vehicle variability (e. g., mileage accumulation and associated control system deterioration), test procedure
differences (e.g., different evaporative test procedures-multiday vs Ih diurnal-with associated impacts on
                                             38

-------
exhaust emissions, and different facility specifications-sampling systems, pressure/altitude, temperature, and
humidity), and detailed fuel differences (e.g., compositional differences including differences in the gasoline
component of alcohol-gasoline blends). All RFG, CNG, M85, and E85 fuels are not created equal. The
Kelly studies cited below involve much larger numbers of vehicles than this study, or those of Gabele or
Auto/Oil AQIRP. Care must also be exercised when comparing observed organic emission rates because of
the diverse options for reporting this category of emissions. NMOG mass emission rates include all organics,
excepting methane, with oxygenate oxygen mass; OMHCE mass emission rates include all organics, with the
assumption that each C atom is associated with 1.85 H atoms (i.e., CHj 85), excluding oxygenate oxygen
mass; OMNMHCE mass emission rates include OMHCE, less methane; THC mass emission rates include
only hydrocarbon compounds; and NMHC mass emission rates include only nonmethane hydrocarbon
compounds.
Table 11. Comparison of observed weighted FTP exhaust emission characteristics with other studies.
Vehicle
95 Dodge
Caravan
94 Dodge
Caravan

93 Taurus
FFV


93 Lumina
VFV


93 Spirit
FFV


Fuel
RFG
CNG
%chg
RFG
M85
%chg
RFG
E85
%chg
RFG
M85
%chg
NMOG
g/mi
0.154
0.006
-96
0.116
0.304
+162
0.140
0.244
+74
0.151
0.284
+88
Carter
MIR
sp. react.
3.68
2.93
-20
3.27
1.27
-61
3.26
2.41
-26
3.54
1.21
-66
OMHCE
g/mi
0.198
0.094
-53
0.146
0.191
+31
0.176
0.299
+70
0.201
0.171
-15
OM CO
NMHCE ^
g/mi
1.70
0.53
-69
1.44
2.48
+72
1.97
3.19
+62
3.36
5.14
+53
NOX
g/mi
0.29
0.02
-93
0.18
0.24
+33
0.27
0.18
-33
0.15
0.17
+13
Study
This
study










 91 Lumina
 VFV
RFG   0.20
            M85
            %chg
        0.42
        +110
3.3

1.3
-61
2.46    0.52

4.53    0.29
+84    -44
        Gabele,
         1995
 93 Lumina
 VFV
RFG   0.16
            E85
            %chg
        0.27
        +69
3.5
2.3
-34
1.98    0.27
2.90
+47
0.17
 -37
                                             39

-------
Vehicle
93 Spirit
FFV


93 Taurus
FFV


92 Dodge
B250 Van
92 Dodge
B250Van
93 Chev.
Sierra
93 Spirit
FFV (71
vehicles)


94 Ford
E150 Van
FFV (16
vehicles)

93 Lumina
VFV


92,94
Dodge
B250
Vans
(37
vehicles)

93
FFV/VFV
(6
vehicles)

Fuel
RFG
M85
%chg
RFG
M85
%chg
CNG
CNG
CNG
RFG
M85
%chg
RFG
M85
%chg
RFG

E85
%chg
RFG
CNG
%chg
RFG
M85
%chg
NMOG
g/mi
0.15
0.37
+147
0.12
0.40
+233
0.02
0.60
0.06












0.100
0.209
+109
Carter
MIR
sp. react.
3.3
1.1
-67
3.5
1.25
-64
2.2
0.6
2.55
3.65
1.45
-60
3.7
1.8
-51
3.53

2.48
-30
4.08
2.04
-50
3.42
1.61
-53
OMHCE OM
g/mi NMHCE
g/mi









0.13
0.11
-15
0.15
0.13
-13
0.16

0.12
-25
0.28
0.09
-68
0.126
0.119
-6
CO
g/mi
2.77
2.65
-4
1.31
2.42
+85
0.55
1.46
5.95
1.69
1.64
-3
2.22
1.49
-33
2.80

2.29
-18
4.73
2.60
-45
1.40
1.53
+9
NOX
g/mi
0.08
0.10
+25
0.10
0.18
+80
0.19
1.48
0.39
0.16
0.20
+25
0.76
0.84
+11
0.22

0.16
-27
0.73
0.53
-27
0.32
0.34
+6
Study









Kelly,
etal,
1995a





Kelly,
etal,
1995b

Kelly,
etal,
1995c


Auto/Oil
AQIRP,
1994

40

-------
 Vehicle     Fuel   NMOG     Carter     OMHCE     OM     CO   NOX
                     g/mi      MIR      g/mi    NMHCE   -.   g/mi
                             sp. react.               g/mi
92,93,94
FFV/VFV
(3
vehicles)


RFG



E85
%chg
0.123



0.192
+56
3.37



2.57
-24
0.141



0.175
+24
1.63



2.53
+55
0.45



0.28
-38
Auto/Oil
AQIRP,
1995a



 92 GM
 Sierra
 Truck
RFG


CNG
%chg
3.33

2.61
 -22
0.550    8.93    0.98   Auto/Oil
                        AQIRP,
                         1995b
0.074    7.06    0.25
 -87      -21    -74
 93 Ford
 Crown
 Vic.
RFG
3.39
0.085     1.38    0.34


92 Dodge
B250
Van


CNG
%chg
RFG

CNG
%chg
2.21
-35
3.42

2.125
-34
0.017
-80
0.368

0.040
-89
0.56
-59
8.44

2.31
-73
0.18
-47
0.63

0.69
+10
As indicated, the emission changes resulting from use of different fuels (RFG vs CNG, M85, and E85 fuels)
varies from study to study.  Detailed contrasts cannot be made between this study and the others included in
Table 11 examining CNG fuel, since this program used a lower inertia weight, more advanced, lower
emission OEM vehicle than the others. On changing from RFG to M85 fuel, increased NMOG emission
rates are reported in this study (+88% to +162%), and those of Gabele (+ 110% to +233%) and Auto/Oil
AQIRP (+109%). On changing from RFG to E85 fuel, increased NMOG emission rates are reported in this
study (+74%), and those of Gabele (+69%) and Auto/Oil AQIRP (+56%). A significant fraction of the
alcohol fuel NMOG mass emission rate increase results from oxygen mass. Kelly reported decreases in
OMNMHCE on changing from RFG to M85 fuel (-13% to -15%) and from RFG to E85 fuel (-25%).

The reported specific reactivities of the organic emissions (g O3/ g NMOG), considered an indicator of
relative propensities to produce atmospheric ozone, were similar. This study reported RFG, E85, and M85
fuel weighted FTP exhaust specific reactivities of 3.44,2.41, and 1.24, respectively; Gabele reported
weighted FTP exhaust specific reactivities of 3.40,2.30, and  1.22, respectively; Auto/Oil reported weighted
FTP exhaust specific reactivities of 3.39,2.57, and 1.61, respectively; and Kelly reported weighted FTP
exhaust specific reactivities of 3.74,2.48, and  1.63, respectively.

Observed changes in CO and NOX emissions when fuels are changed also varies.  On changing from RFG to
M85 fuel, increased CO emission rates are reported in this study (+53% to +72%), Gabele observed both
increases and decreases (-4% to +85%), and Auto/Oil AQIRP an increase (+9%). On changing from RFG to
                                             41

-------
E85 fuel, increased CO emission rates are reported in this study (+62%), and by Gabele (447%) and
Auto/Oil AQIRP (+55%). Kelly reported decreases in CO on changing from RFG to M85 fuel (-3% to
-33%) and from RFG to E85 fuel (-25%).


                                     Conclusions

The potential to influence motor vehicle emissions and the atmospheric chemistry of the emissions by
changing fuel composition is examined for RFG, M85, E85, and CNG fuels. Test vehicles included a 1995
conventional fuel Dodge Caravan and a similar 1994 vehicle designed for dedicated use of CNG fuel, a 1993
Ford Taurus and a 1993 Dodge Spirit designed for flexible mixtures of methanol and gasoline (0 to 85%
methanol), and a 1993 Chevrolet Lumina designed for flexible mixtures of ethanol and gasoline (0 to 85%
ethanol). Both exhaust and evaporative emissions are examined in close accord with the FTP, and exhaust
emissions are also examined with a high speed, high acceleration rate "off-cycle" driving schedule (REP05).
This represents a rather limited test matrix (the number of vehicles and fuels examined limited by available
resources), and the observations and conclusions may not be representative of the specific technologies.
However, when examined with a number of similar studies, this program will contribute to collective
conclusive observations. Under FTP driving conditions, CNG fuel resulted in a large decrease of total
(exhaust plus evaporative) NMOG emissions when compared to RFG fuel. The Dodge Caravan NMOG
emission rate with CNG fuel is reduced about 98% from the rate observed with RFG fuel. The Ford Taurus,
with an evaporative emissions control malfunction condition, also benefited from the use of alternative fuel.
A 42% evaporative NMOG emission rate reduction is observed with M85 fuel.  A similar set of observations
exists for emissions ozone potential (mg ozone per mi traveled) as estimated by Carter MIR. The  Carter
ozone potential of the Dodge Caravan emissions is reduced about 99% with CNG fuel versus RFG fuel.  The
Ford Taurus emissions ozone potential is reduced about 34% with M85 fuel versus RFG fuel. Combined
FTP toxic compound  emissions (benzene, formaldehyde, acetaldehyde, and 1,3-butadiene) are greater with
M85 and E85 fuels than with RFG fuel, and less with CNG fuel than RFG fuel.  Benzene is the most
abundant emitted toxic compound with RFG fuel, formaldehyde with M85 fuel, and acetaldehyde with E85
fuel. FTP MPG fuel economies are reduced with M85 and E85 fuels compared to RFG fuel, as expected
based upon the relative combustion efficiencies and energy contents (BTU/gal) of the fuels.  Improved
efficiencies are observed with all the alternative fuels (CNG, M85, E85) compared to that observed with RFG
fuel.

Under the high speed and high acceleration rate driving conditions of the REP05 cycle, Carter MIR ozone
potential reductions are observed for all the alternative fuels versus RFG fuel, except for the Dodge Spirit
FFV with M85 fuel. The ozone potential reduction is greatest with CNG fuel. A notable difference in toxic
emissions is observed for all fuels under REP05  high acceleration rate driving conditions. The benzene
emission rate is dramatically elevated, becoming the most abundant toxic compound emission with all fuels
studied.

The potential to influence atmospheric ozone and toxic compound concentrations by changing fuel
composition is further examined by irradiating vehicle exhaust in a photochemical reaction chamber. Carter
maximum incremental reactivity (MIR) based specific reactivity (i.e., mg O3/mg NMOG, CO, and  CH4),
chamber 12 h ozone concentration, and dNO/dt at chamber NO-NO2 concentration crossover, suggest that
RFG exhaust ozone reactivity ~ E85 exhaust ozone reactivity > M85 exhaust ozone reactivity > CNG
exhaust ozone reactivity per unit of NMOG, CO, and CH4 mass emissions. Under the program test
conditions (i.e., vehicles, fuels, and driving scenarios), the ozone producing potential of CNG exhaust is
about 1/5 that of RFG and E85 exhaust per unit of mass emissions; and the ozone producing potential of
M85 exhaust is about 1/2 that of RFG and E85 exhaust per unit mass emissions. Observed chamber toxic
compound concentrations after 12 h exhaust irradiations included PAN substantially lower with M85 (2.2
ppbv) and CNG (1.2 ppbv) fuels than with RFG (20.4 ppbv) and E85 (24.5) fuels, and acetaldehyde

                                             42

-------
 substantially higher with E85 (68.3 ppbv) fuel than RFG (16.5 ppbv), M85 (5.1 ppbv), or CNG (10.9 ppbv)
 fuels, and formaldehyde higher with E85 (105 ppbv) and CNG (97.5 ppbv) fuels than with RFG (65.1 ppbv)
 and M85 (67.5) fuels.

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                                              44

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Russell, A.G., D. St. Pierre, and J.B. Milford (1991): "Ozone Control and Methanol Fuel Use," Science 247,
201-205.

Russell, A., Milford, J., Bergin, M. S., McBride, S., McNair, L.,Yang, Y., Stockwell, W. R., and B. Croes
(1995): "Urban Ozone Control and Atmospheric Reactivity of Organic Gases," Science, 269,491-495.


                                              45

-------
 Sexton, K. and P.B. Ryan (1988): "Assessment of Human Exposure to Air Pollution: Methods,
 Measurements, and Models," In: Air Pollution, the Automobile, and Public Health. Eds. A.Y. Watson, R.R.
 Bates, and D. Kennedy. National Academy Press, Washington, D.C. pp. 99-132.

 Siegl, W. O., Richert, J. F. O., Jensen, T. E., Schuetzle, D., Swarin, S.  J., Loo, J. F., Prostak, A., Nagy, D.,
 and A. M. Schlenker (1993): "Improved Emissions Speciation Methodology for Phase n of the Auto/Oil
 AQIRP-Hydrocarbons and Oxygenates," SAE 930142, Warrendale, PA.

 Smith, D.F., T.E. Kleindienst, E.E. Hudgens, C.D. Mclver, and J.J. Bufalini (1991): "The photooxidation of
 methyl tert/ary-butyl ether," Int. J. Chem. Kinet. 23,907-924.

 Society of Automotive Engineers (1992-1995): Auto/Oil AQIRP Publication Series, SP-920, SP-1000,
 Society of Automotive Engineers, Warrendale PA.

 Stump, F., Tejada, S., Black, F., Ray, W., Crews, W., and R. Davis (1995): "Compound Injection to Assure
 the Performance of Motor Vehicle Emissions Sampling Systems," in review, Society of Automotive
 Engineers, Warrendale PA.

 Tejada, S. B. (1986): "Evaluation of Silica Gel Cartridges Coated In Situ with Acidified
 2,4-Dinitrophenylhydrazine for Sampling Aldehydes and Ketones in Air",  Intern. J. Environmental Anal.
 Chem., Vol. 26, pp 167-185; also described in ASTM D5197-92, "Standard Test Method for Determination
 of Formaldehyde and Other Carbonyl Compounds in Air (Active Sampler Methodology).

 U.S. EPA (1994): "Mobile Source Emission Factor Model, MOBILE 5A," Office of Mobile Sources, Ann
 Arbor, ML

 U.S. Congress (1988): "Alternative Motor Fuels Act of 1988," 100th Congress, Public Law 100-494,102
 STAT. 2441, US Government Printing Office, Washington, DC.
                                                                  >\
 U.S. Congress (1990): "Clean Air Act Amendments of 1990, Title H-Provisions Relating to Mobile Sources,"
 101st Congress, Public Law 101-549,104  STAT. 2399, US Printing Office, Washington, DC.

 Watson A.Y., Bates R.R. and Kennedy D., eds. (1988): "Air Pollution, the Automobile, and Public Health,"
 National Academy Press, Washington, D.C.

 Yang, Y-J., W.R. Stockwell, J.B. Milford (1995): "Uncertainties in Incremental Reactivities of Volatile
 Organic Compounds," Environ. Sci. Technol., 29,1336-1345.

 Zweidinger, R. A., Crews, W., Braddock, J. A. (1993): "Research Protocol Method for Analysis of
Oxygenated Compounds Emitted from Automobiles or Present in Automobile Fuels by Gas
Chromatography," USEPA, MSERB, Research Triangle Park, NC.
                                             46

-------
                                      Glossary
 AQIRP       Air Quality Improvement Research Program




 CARS        California Air Resources Board




 CFM         Cubic Feet per Minute




 CFR         Code of Federal Regulations




 CNG         Compressed Natural Gas




 CO           Carbon Monoxide




 CO2          Carbon Dioxide




 CRC         Coordinating Research Council




 CVS          Constant Volume Sampling system




 DNPH        Dinitrophenylhydrazine




 DOE         Department of Energy




 E85           Ethanol 85%, Gasoline 15% Fuel




 E1CD          Electron Capture Detector




 EPA          Environmental Protection Agency




 FID           Flame lonization Detector




 FTP           Federal Test Procedure




 GC           Gas Chromatograph




 HC           Hydrocarbon




 HFID         Hot Flame lonization Detector




 M85           Methanol 85%, Gasoline 15% Fuel




 MIR           Maximum Incremental Reactivity




 MOR         Maximum Ozone Reactivity




MTBE        Methyl Tertiary Butyl Ether







                                          47

-------
 NAAQS       National Ambient Air Quality Standard

 NERL         National Exposure Research Laboratory

 NMOG        NonMethane Organic Gas (includes oxygen mass)

 NOX          Oxides of Nitrogen (nitrogen oxide plus nitrogen dioxide)

 O3            Ozone

 OMHCE       Organic Matter Hydrocarbon Equivalent (assumes all organic carbon associated with 1.85
               hydrogen atoms (i.e., CH[ 85) for calculation of mass emission rates)

 ppmv          Parts per Million Volume (similarly ppbv and pptv are parts per billion and parts per trillion
               volume)


 FDD           Programmable Interface Device

 RAF          Reactivity Adjustment Factor

 REP05         High speed, high acceleration rate driving schedule

 RFG          Reformulated Gasoline Fuel

 RH            Relative Humidity

 ROG          Reactive Organic Gases (used in this study to reference irradiation chamber reactive organic
               concentrations in ppmC or ppbC)

 RVP          Reid Vapor Pressure

 SAE          Society of Automotive Engineers

 SCFM         Standard Cubic Feet per Minute

 SHED         Sealed Housing for Evaporative emissions Determination

 TCTC         Temperature Controlled Test Chamber

THC          Total Hydrocarbon

UDDS         Urban Dynamometer Driving Schedule

ULEV         Ultra Low Emission Vehicle

UV            Ultraviolet

VOC          Volatile Organic Compound
                                             48

-------
APPENDIX A: Test Fuel Composition
COMPOUND
ALKANES
ALKENES
AROMATICS
OXYGENATES
UNKNOWNS
METHANE
ETHANE
PROPANE
ISOBUTANE
ISO-BUTYLENE
N-BUTANE
TRANS-2-BUTENE
aS-2-BUTENE
3-METHYL-l-BUTENE
ISO-PENTANE
1,4-PENTADIENE
1-PENTENE
2-METHYL-l-BUTENE
N-PENTANE
ISOPRENE
TRANS-2-PENTENE
aS-2-PENTENE
2-METHYL-2-BUTENE
TRANS-1.3-PENTADIENE
2,2-DIMETHYLBUTANE
CYCLOPENTENE
RFG,
VOL%
59.154
6.242
23.478
11.075
0.051




0.394
1.448

0.014
0.018
12.415

0.115
0.239
1.416
0.009
0.352
0.198
0.630
0.006
0.089
0.066
RFG,
PPMC
%
54.650
6.150
30.060
9.070
0.070




0.326
1.127

0.012
0.016
10.426

0.103
0.216
1.201
0.009
0.316
0.181
0.582
0.006
0.078
0.074
M85,
VOL%
11.807
0.669
3.115
84.398
0.012



0.029
0.004
4.191



1.504
0.002
0.013
0.028
0.172
0.001
0.047
0.024
0.077

0.010
0.010
M85,
PPMC
%
18.440
1.170
7.110
73.240
0.030



0.039
0.006
5.831



2.257
0.004
0.021
0.046
0.261
0.002
0.075
0.039
0.127

0.016
0.019
E85,
VOL%
10.609
0.775
3.347
85.264
0.004




0.060
1.493
0.014
0.008
0.003
1.708

0.015
0.030
0.686

0.047
0.025
0.071

0.094
0.008
E85,
PPMC
%
13.64
1.10
5.94
79.28
0.04




0.069
1.616
0.016
0.009
0.004
1.993

0.019
0.038
0.809

0.059
0.031
0.091

0.114
0.012
CNG,
PPMC
%
99.84
0.02
0.14
0.0
0.0
93.440
4.610
0.850


0.320



0.090











              A-l

-------
COMPOUND
3-METHYL-l-PENTENE
CYCLOPENTANE
2,3-DIMETHYLBUTANE
4-METHYL-aS-2-PENTENE
2-METHYLPENTANE
3-METHYLPENTANE
2-METHYL-l-PENTENE
1-HEXENE
N-HEXANE
CIS-3-HEXENE
TRANS-2-HEXENE
2-METHYL-2-PENTCNE
aS-3-METHYL-2-PENTENE
4-METHYLCYCLOPENTENE
QS-2-HEXENE
TRANS-3-METHYL-2-PENTENE
METHYLCYCLOPENTANE
2,4-DIMETHYLPENTANE
2,2,3-TRIMETHYLBUTANE
C7H12
2,4-DIMETH YL- 1 -PENTENE
1 -METHYLCYCLOPENTENE
BENZENE
3,3-DIMETHYLPENTANE
TRANS-2-METHYL-3-HEXENE
CYCLOHEXANE
C7H14
2-METHYLHEXANE
RFC,
VOL%
0.063
0.061
1.118
0.035
1.605
1.144
0.112
0.067
0.895
0.141
0.198
0.292
0.138
0.025
0.113
0.215
0.446
3.222
0.036
0.004
0.011
0.188
0.751
0.094
0.009
0.098
0.026
1.203
RFC,
PPMC
%
0.059
0.063
1.007
0.033
1.426
1.034
0.106
0.063
0.820
0.134
0.185
0.279
0.132
0.027
0.108
0.207
0.465
2.959
0.034
0.005
0.011
0.208
0.988
0.089
0.009
0.106
0.026
1.115
M85,
VOL%
0.009
0.007
0.137
0.006
0.213
0.139
0.023

0.114
0.019
0.025
0.034
0.021

0.013
0.025
0.057
0.415
0.003
0.001
0.001
0.023
0.102
0.014

0.011

0.163
M85,
PPMC
%
0.015
0.014
0.220
0.010
0.338
0.225
0.039

0.187
0.032
0.042
0.058
0.036

0.023
0.044
0.107
0.682
0.005
0.001
0.002
0.045
0.239
0.023

0.022

0.271
E85,
VOL%
0.009
0.035
0.255
0.006
0.459
0.320
0.025

0.368
0.023
0.030
0.039
0.023

0.016
0.029
0.156
0.375
0.003
0.002
0.002
0.028
0.143
0.021

0.075
0.005
0.205
E85,
PPMC
%
0.011
0.050
0.319
0.007
0.567
0.402
0.033

0.469
0.030
0.039
0.051
0.030

0.021
0.039
0.226
0.479
0.004
0.003
0.003
0.043
0.262
0.027

0.114
0.007
0.264
CNG,
PPMC
%

0.010
0.010

0.030
0.020


0.030







0.020





0.060


0.020


A-2

-------
COMPOUND
2.3-DIMETHYLPENTANE
1 , 1 -DIMETHYLCYCLOPENTANE
3-METHYLHEXANE
TRANS-5-METHYL-2-HEXENE
OS- 1 ,3-DIMETHYLCYCLOPENTANE
TRANS-1.3-DIMETHYLCYCLOPENTANE
ISO-OCTANE
3-METHYL-TRANS-3-HEXENE
TRANS-3-HEPTENE
N-HEPTANE
aS-3-METHYL-3-HEXENE
TRANS-2-HEPTENE
3-ETHYL-2-PENTENE
2-METHYL-2-HEXENE
1 ,5-DIMETHYLCYCLOPENTENE
4-ETHYL CYCLOPENTENE
METYHLCYCLOHEXANE
1 , 1,3-TRIMETHYLCYCLOPENTANE
C8H14
2,5-DIMETHYLHEXANE
2,4-DIMETHYLHEXANE
1 ,2,4-TRIMETHYLCYCLOPENTANE
C8H16
C.T.C- 1 ,2,3-TRIMETHYLC YCLOPENTANE
2,3,4-TRIMETHYLPENTANE
1-ETHYLCYCLOPENTENE
TOLUENE
2,3-DIMETHYLHEXANE
RFC,
VOL%
5.238
0.031
1.281
0.044
0.149
0.257
11.846
0.031
0.066
0.813
0.268
0.063
0.027
0.070
0.104
0.009
0.220
0.041
0.008
0.895
1.657
0.128
0.026
0.055
3.142
0.057
5.203
0.964
RFC,
PPMC
%
4.970
0.033
1.202
0.042
0.154
0.266
11.217
0.030
0.065
0.759
0.265
0.062
0.027
0.069
0.115
0.010
0.236
0.043
0.009
0.849
1.588
0.135
0.027
0.058
3.093
0.065
6.696
0.940
M85,
VOL%
0.689
0.005
0.170
0.018
0.021
0.035
1.505
0.004
0.009
0.106
0.034
0.008
0.004
0.010
0.014

0.030
0.006

0.118
0.220
0.018
0.003

0.412
0.007
0.674
0.123
M85,
PPMC
%
1.168
0.009
0.285
0.031
0.038
0.065
2.547
0.008
0.016
0.176
0.060
0.015
0.006
0.017
0.027

0.058
0.011

0.200
0.376
0.034
0.006

0.725
0.014
1.550
0.214
E85,
VOL%
0.685
0.012
0.222
0.011
0.033
0.051
1.336
0.008
0.013
0.156
0.045
0.012
0.006
0.013
0.019

0.055
0.007
0.002
0.110
0.207
0.018
0.004
0.008
0.370
0.009
0.859
0.123
E85,
PPMC
%
0.904
0.018
0.290
0.014
0.048
0.073
1.759
0.012
0.018
0.203
0.062
0.016
0.008
0.017
0.029

0.082
0.011
0.003
0.146
0.276
0.027
0.005
0.012
0.507
0.014
1.536
0.167
CNG,
PPMC
%
0.020

0.010



0.010



0.020





0.030









0.020

A-3

-------
COMPOUND
2-METHYLHEPTANE
4-METHYLHEPTANE
3,4-DIMETHYLHEXANE
3-METHYLHEPTANE
TRANS-1.4-DIMETHYLCYCLOHEXANE
2,2,5-TRIMETHYLHEXANE
1-OCTENE
CIS-l-ETHYL-3-METHYLCYCLOPENTANE
C8H16
C8H16
C8H16
N-OCTANE
C8H16
C8H16
2-OCTENE
*** UNKNOWN ***
2,3.5-TRIMETHYLHEXANE
C8H14
2,4-DIMETHYLHEPTANE
C8H14
2,6-DIMETHYLHEPTANE
n-PROPYLCYCLOPENTANE
2,5-DIMETHYLHEPTANE
1 , 1 ,4-TRIMETH YLCYCLOHEXANE
C9H18
ETHYLBENZENE
2,3-DIMETHYLHEPTANE
M&P-XYLENE
RFC,
VOL%
0.707
0.309
0.260
0.791
0.108
1.069
0.041
0.101
0.062
0.078
0.079
0.632
0.083
0.101
0.104
0.028
0.168
0.026
0.103
0.044
0.115
0.054
0.190
0.036
0.061
2.481
0.121
5.658
RFC,
PPMC
%
0.676
0.298
0.254
0.766
0.115
1.037
0.041
0.109
0.065
0.082
0.084
0.607
0.088
0.107
0.105
0.029
0.166
0.029
0.100
0.049
0.112
0.058
0.188
0.039
0.067
3.168
0.120
7.200
M85,
VOL%
0.093
0.040
0.039
0.104
0.015
0.142
0.005
0.013
0.009
0.010
0.011
0.083
0.012
0.027

0.004
0.026

0.014
0.005
0.015
0.007
0.024
0.005
0.008
0.312
0.015
0.720
M85,
PPMC
%
0.160
0.069
0.069
0.180
0.029
0.247
0.009
0.026
0.017
0.020
0.020
0.143
0.022
0.050

0.007
0.047

0.024
0.011
0.025
0.013
0.043
0.009
0.015
0.712
0.027
1.638
E85,
VOL%
0.100
0.050
0.032
0.111
0.014
0.171

0.014

0.020
0.013
0.087
0.013
0.033

0.004
0.034

0.014
0.007
0.017
0.009
0.047
0.007
0.010
0.355
0.016
0.825
E85,
PPMC
%
0.133
0.066
0.043
0.149
0.020
0.231

0.021

0.029
0.019
0.116
0.019
0.049

0.006
0.046

0.019
0.011
0.022
0.014
0.064
0.010
0.016
0.631
0.022
1.460
CNG,
PPMC
%
0.010


0.010

0.010





0.010













0.010

0.020
A-4

-------
COMPOUND
3-METHYLOCTANE
C9H18
C10H22
1-NONENE
O-XYLENE
C9H18
C9H18?
N-NONANE
C9H18
C9H18
C9H18
C9H18
ISOPROPYLBENZENE
C10H22?
n-BUTYLCYCLOPENTANE
C10H22
C9H18
C10H22 ?
C10H20
N-PROPYLBENZENE
l-METHYL-3-ETHYLBENZENE
l-METHYL-4-ETHYLBENZENE
C10H22
1 ,3,5-TRIMETHYLBENZENE
C10H22
1 -METHYL-2-ETHYLBENZENE
C10H20
C10H20
RFC,
VOL%
0.310
0.067
0.141
0.661
1.802
0.061
0.026
0.174
0.118
0.010
0.066
0.074
0.117
0.065
0.033
0.083
0.036
0.038
0.021
0.421
1.299
0.588
0.058
0.700
0.077
0.450
0.033
0.028
RFC,
PPMC
%
0.305
0.073
0.140
0.668
2.336
0.067
0.029
0.171
0.130
0.010
0.073
0.082
0.148
0.065
0.036
0.082
0.040
0.038
0.023
0.530
1.635
0.737
0.058
0.886
0.077
0.577
0.036
0.031
M85,
VOL%
0.041
0.013
0.023
0.011
0.226
0.008
0.003
0.021
0.014

0.009
0.010
0.015
0.008
0.004
0.011
0.005
0.004

0.049
0.164
0.079
0.007
0.088
0.008
0.051

0.003
M85,
PPMC
%
0.072
0.025
0.040
0.020
0.524
0.015
0.006
0.037
0.027

0.017
0.019
0.034
0.014
0.007
0.019
0.010
0.008

0.110
0.368
0.176
0.012
0.198
0.015
0.116

0.006
E85,
VOL%
0.039
0.012
0.029
0.012
0.277
0.007
0.004
0.020
0.026
0.002
0.010
0.015
0.017
0.007
0.003
0.013
0.002
0.004
0.003
0.044
0.137
0.062

0.116
0.005
0.048
0.006
0.004
E85,
PPMC
%
0.054
0.018
0.040
0.017
0.499
0.011
0.005
0.028
0.040
0.002
0.015
0.024
0.029
0.010
0.004
0.019
0.003
0.005
0.004
0.077
0.240
0.109

0.203
0.007
0.086
0.009
0.006
CNG,
PPMC
%




0.010























A-5

-------
COMPOUND
C10H20
o-METHYLSTYRENE
1 ,2,4-TRIMETHYLBENZENE
N-DECANE
2-METHYLPROPYLBENZENE
1-METHYLPROPYLBENZENE
C11H24
1,2,3-TRIMETHYLBENZENE
C11H24
2,3-DIHYDROINDENE(INDAN)
1.3-DIETHYLBENZENE
l-METHYL-3-n-PROPYLBENZENE
1 ,2-DIETHYLBENZENE
C11H24
C11H24
1 -METH YL-2-n-PROPYLBENZENE
1 .3-DIMETHYL-4-ETHYLBENZENE
l,2-DIMETHYL-4-ETHYLBENZENE
1 .3-DIMETHYL-2-ETHYLBENZENE
C10H12
C11H22
n-UNDECANE
C11H16
1 .2-DIMETHYL-3-ETHYLBENZENE
*** UNKNOWN ***
1 ,2,4,5-TETRAMETHYLBENZENE
1 ,2,3,5-TETRAMETHYLBENZENE
C11H16
RFC,
VOL%

0.027
1.632
0.088
0.045
0.046
0.014
0.319
0.036
0.160
0.139
0.261
0.456
0.020
0.045
0.099
0.133
0.125
0.230
0.049
0.020
0.043
0.022
0.058
0.007
0.105
0.143
0.039
RFC,
PPMC
%

0.036
2.092
0.088
0.057
0.057
0.014
0.416
0.036
0.229
0.174
0.325
0.584
0.020
0.046
0.125
0.168
0.158
0.296
0.067
0.021
0.044
0.027
0.075
0.008
0.128
0.185
0.049
M85,
VOL%
0.001

0.211
0.011
0.006
0.005
0.002
0.042
0.003
0.023
0.021
0.036
0.064
0.003
0.008
0.013
0.019
0.018
0.034
0.006
0.003
0.005
0.006
0.010
0.003
0.020
0.034

M85,
PPMC
%
0.002

0.484
0.020
0.013
0.012
0.003
0.098
0.006
0.058
0.047
0.080
0.147
0.005
0.014
0.029
0.044
0.041
0.079
0.016
0.006
0.010
0.014
0.023
0.007
0.044
0.078

E85,
VOL%


0.168
0.014
0.004
0.004
0.002
0.030
0.005
0.016
0.016
0.026
0.048
0.003
0.007
0.011
0.014
0.014
0.024
0.006

0.003
0.003
0.006

0.010
0.013
0.004
E85,
PPMC
%


0.299
0.020
0.008
0.006
0.003
0.055
0.007
0.032
0.028
0.045
0.085
0.004
0.010
0.019
0.024
0.025
0.043
0.012

0.005
0.006
0.011

0.017
0.024
0.006
CNG,
PPMC
%


0.010




0.010




















A-6

-------
COMPOUND
C11H16
C11H16
**« UNKNOWN ***
C10H12
C11H16
C10H12
C11H16
C11H16
C11H16
C10H12
C11H14
NAPHTHALENE
n-DODECANE
MTBE
METHANOL
ETHANOL
RFC,
VOL%
0.026
0.040

0.081
0.034
0.143
0.041
0.042
0.014
0.021

0.153
0.027
11.437


RFC,
PPMC
%
0.033
0.050

0.113
0.042
0.197
0.052
0.052
0.018
0.029

0.239
0.028
9.387


M85,
VOL%
0.005
0.005
0.005
0.015
0.003
0.023
0.003
0.004

0.002
0.002
0.011
0.003
1.168
83.580

M85,
PPMC
%
0.011
0.010
0.012
0.038
0.008
0.057
0.006
0.008

0.005
0.004
0.032
0.006
1.714
72.103

E85,
VOL%
0.002
0.004

0.008
0.003
0.012
0.004
0.006

0.003

0.005

1.614

83.650
E85,
PPMC
%
0.004
0.007

0.015
0.006
0.023
0.007
0.011

0.005

0.011

1.842

77.858
CNG,
PPMC
%
















A-7

-------
         APPENDIX B: Ozone Potential (Carter MIR)

The following pages provide graphic illustrations of ozone potential for each vehicle-fuel pair, for
both FTP and REP05 driving simulations. The presented data are based on Carter MIR
calculations.  Exhaust and evaporative emissions data, along with their sums, are presented for the
FTP simulations; and high speed and high acceleration rate data, along with their composites, are
presented for the REP05 simulations. The composite REP05 results are based on time weighted
sums of the modal results. Data are presented to illustrate the relative contributions of alkane,
alkene, aromatic, alkyne, alcohol/ether, aldehyde/ketone organic compounds, and carbon
monoxide to the emissions ozone potential.
                                       B-l

-------
 E

 en




 I
 c
 a.
 
c
o
N
O
500 -

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
EXHAUST
88.4
123.4
157.3
1.2
2.8
27.4
77.7
EVAPORATIVE
SS7.7
312.0
381 .2
0.0
43.6
0.0
0.0
TOTAL
606.1
435.5
538.5
1.2
46.4
27.0
77.7
                                               Taurus, FTP, M85 Fuel


                                              2,000
                                              1,500 -
                                              1,000 -
                                               500 -

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
EXHAUST
24.2
37.1
77.1
0.2
136.8
109.5
133.9
EVAPORATIVE
238.1
82.0
268.1
0.0
42.4
0.0
0.0
TOTAL
262.3
119.1
345.2
0.2
181.2
109.5
133.9
                                      B-2

-------
     Lumina, FTP. RFG Fuel

     1,200
.E
05

E
I
a.
o


I
                                           Lumina, FTP, E85 Fuel
                                          1,200

ALKANES
ALKENES
AROMATIC8
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDE6/KETONES
CARBON MONOXIDE
EXHAUST
86.6
183.4
15B.B
o.e
4.1
22.1
108.3
EVAPORATIVI
129.9
S9.2
238.2
0.0
11.5
0.0
0.0
TOTAL
J18.5
242.8
398.9
0.8
16.8
22.1
108.3

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALOEHYDES/KETONES
CARBON MONOXIDE
EXHAUST
38.7
157.3
58.7
0.7
199.2
136.3
172.2
EVAPORATIVE
66.3
15.2
69.5
0.0
59.6
0.0
0.0
I TOTAL
93.0
172.6
118.2
0.7
268.8
136.3
172.2
|
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O
     Caravan, FTP, RFG Fuel

     1.000
      800 -
600 -
      400 -
200 -
                                          Caravan, FTP, CNG Fuel

                                          1,000

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
EXHAUST
79.3
187.1
268.7
6.B
2.4
26.0
92.0
EVAPORATIVE TOTAL
81.2
46.9
172.8
0.0
4.8
0.0
0.0
160.6
234.0
441.5
5.9
7.2
26.0
02.0
                                           800
600
                                           400
200

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
EXHAUST
3.2
8.3
0.4
0.0
0.0
6.2
29.1
EVAPORATIVI
0.0
0.0
0.0
0.0
0.0
0.0
0.0
TOTAL
3.2
8.3
0.4
0.0
0.0
6.2
29.1
                                   B-3

-------
 E
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 o
 a.
 s
 o
     Spirit, REP05, RFG Fuel
      5,000
      4.000 -
3.000 -
      2.000 -
1.000 -

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REPOS-1
27.5
42.5
51 .0
0.1
0.0
98.2
1S7.7
REP05-2
211.0
1.428.8
784.4
0.8
0.0
23.3
1326.8
COMPOSITE
54.4
245.6
158.4
0.2
0.0
87.2
385.0
                                              Spirit, REP05, M85 Fuel
                                               5,000
                                               4.000 -
3.000 -
                                               2,000 -
1,000 -

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REPOS-1
8.2
31.9
10.9
0.0
2.9
144.4
208.8
REP05-2
130.1
582.4
288.7
0.0
35.1
113.2
3.421.7
COMPOSITE
28.1
109.5
48.7
0.0
7.8
138.8
877.3
o>
E
o
Q.
O
N
O
    Taurus, REP05, RFG Fuel

      6,000

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REP05-1
52.3
81.0
73.8
0.0
10.8
46.9
158.2
REP05-2
412.6
725.7
813.8
0.0
0.0
16.5
2,849.6
COMPOSITE
105.1
158.4
207.0
0.0
9.1
42.4
523.1
                                             Taurus, REP05, M85 Fuel
                                              6.000
                                                    5,000
                                                    4,000
                                                    3.000
                                                    2,000
                                                    1.000

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REP05-1
4.5
8.6
13.0
0.0
32.8
137.3
91.8
REPOS-2
65.0
128.8
199.4
0.0
24.5
14.3
1.981.5
COMPOSITE
16.3
24.4
40.3
0.0
31.6
119.3
368.5
                                     B-4

-------
    Lumina, REP05, RFC Fuel

     10,000
^»

E



1"
c

£
o
a.

a>

o
N

O
                                          Lumina, REP05, E85 Fuel

                                           10,000

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REPOS-1
38.8
67.C
84.5
0.0
0.0
eo.o
208.3
REP05-2
604.2
1.751.3
1.301.8
0.8
0.0
11.0
4.593.2
COMPOSITE
121.4
314.1
245.7
0.1
0.0
52.8
848.7
                                            8,000







                                            6,000







                                            4,000







                                            2,000

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REPOS-1
8.3
44.4
8.3
0.0
1.6
78.7
178.7
REP05-2
37.8
736.1
168.5
0.0
0.8
62.8
3,176.0
COMPOSITE
10.9
145.7
29.8
0.0
1.4
74.9
617.6
 J
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 C

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 o
   Caravan, REP05, RFG Fuel


      500
      400 -
      300 -
200 -
100 -
                                         Caravan, REP05, CNG Fuel


                                            500

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REP05-1
32.7
38.6
59.6
0.0
0.0
67.8
74.5
REPOS-2
52.0
56.3
137.7
0.0
0.0
7.5
166.8
COMPOSITE
35.6
41.7
71.0
0.0
0.0
59.0
88.3
                                            400
                                            300
200
100

ALKANES
ALKENES
AROMATICS
ALKYNES
ALCOHOLS/ETHERS
ALDEHYDES/KETONES
CARBON MONOXIDE
REPOS-1
1.4
0.7
0.0
0.0
0.0
23.5
9.2
REPOS-2
3.9
7.5
7.6
0.0
0.0
6.0
50.2
COMPOSITE
1.8
1.7
1.2
0.0
0.0
21.0
15.2
                                   B-5

-------
   APPENDIX C: Detailed Emissions Composition and
              Carter Ozone Reactivity Summaries
The following Tables present exhaust and evaporative emissions composition summaries (average of 2 or
more tests) for each vehicle-fuel pair examined in this program. Results are presented for both FTP and
REP05 driving simulations.  For FTP tests, exhaust results are reported with test phases 1, 2, and 3 weighted
according to CFR practice; and evaporative results with diurnal and hot soak emissions weighted according to
practice described in the EXPERIMENTAL section of this report. For REP05 tests, exhaust results are
reported for phases 1,2, and the composite of these phases. NMOG emissions are distributed among organic
classes including alkanes, alkenes, aromatics, alkynes, alcohols/ethers, and aldehydes/ketones.  Both Carter
ozone potential (mg ozone per mi) and specific reactivities (mg ozone per mg NMOG) are presented for each
NMOG organic group, CH4 and CO. Detailed HC compositions (often > 300 compounds) are available from
the authors on computer magnetic media.
                                      C-l

-------
Dodge Caravan, RFG fuel
FTP WTO-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
64.90
26.38
51.01
3.61
0.16
3.82
4.39
154.27
1703.77
26.45
1884.49
OZONE, mg/mi
MIR
79.30
187.08
268.75
5.91
0.00
2.37
24.96
568.38
92.00
0.40
660.78
MOR
47.34
74.65
78.52
2.94
0.00
1.57
7.00
212.01
64.74
0.25
277.00
O3/NMOG, mg/mg
MIR
1.22
7.09
5.27
1.64
0.00
0.62
5.68
3.68
0.05
0.02
0.35
MOR
0.73
2.83
1.54
0.81
0.00
0.41
1.59
1.37
0.04
0.01
0.15
FTP WTD-EVAPORATIVE
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
69.03
7.48
32.74
0.00
0.38
7.72
0.00
117.34
0.00
0.00
117.34
OZONE, mg/mi
MIR
81.16
46.93
172.76
0.00
0.00
4.79
0.00
305.64
0.00
0.00
305.64
MOR
50.46
17.66
50.00
0.00
0.00
3.16
0.00
121.28
0.00
0.00
121.28
03/NMOG, mg/mg
MIR
1.18
6.28
5.28
0.00
0.00
0.62
0.00
2.60
0.00
0.00
2.60
MOR
0.73
2.36
1.53
0.00
0.00
0.41
0.00
1.03
0.00
0.00
1.03
FTP EXHAUST AND EVAPORATIVE SUMMATION
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
133.92
33.85
83.75
3.61
0.54
11.54
4.39
271.62
1703.77
26.45
2001.83
OZONE, mg/mi
MIR
160.47
234.02
441.51
5.91
0.00
7.16
24.96
874.02
92.00
0.40
966.42
MOR
97.80
92.31
128.52
2.94
0.00
4.73
7.00
333.30
64.74
0.25
398.29
O3/NMOG, mg/mg
MIR
1.20
6.91
5.27
1.64
0.00
0.62
5.68
3.22
0.05
0.02
0.48
MOR
0.73
2.73
1.53
0.81
0.00
0.41
1.59
1.23
0.04
0.01
0.20
C-2

-------
Dodge Caravan, CNG fuel
FTP WTD-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
rag/mi
EMISSION
3.72
1.21
0.08
0.00
0.00
0.00
0.78
5.79
538.00
102.49
646.28
OZONE, mg/mi
MIR
3.16
8.25
0.39
0.00
0.00
0.00
5.16
16.96
29.05
1.54
47.55
MOR
1.91
3.39
0.12
0.00
0.00
0.00
1.54
6.96
20.44
0.95
28.36
O3/NMOG, mg/mg
MIR
0.85
6.84
4.77
0.00
0.00
0.00
6.61
2.93
0.05
0.02
0.07
MOR
0.51
2.81
1.47
0.00
0.00
0.00
1.97
1.20
0.04
0.01
0.04
Note: There were no evaporative emissions with this vehicle technology.
                                                   C-3

-------
Ford Taurus, RFG fuel
FTPWTD-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/nri
EMISSION
54.97
19.00
31.11
1.79
0.06
4.55
4.89
116.37
1439.45
13.69
1569.51
OZONE, mg/mi
MIR
68.43
123.44
157.32
1.16
0.00
2.82
27.39
380.56
77.73
0.21
458.50
MOR
41.02
48.88
45.82
0.73
0.00
1.87
8.21
146.52
54.70
0.13
201.35
O3/NMOG, mg/mg
MIR
1.24
6.50
5.06
0.65
0.00
0.62
5.60
3.27
0.05
0.02
0.29
MOR
0.75
2.57
1.47
0.40
0.00
0.41
1.68
1.26
0.04
0.01
0.13
FTP WTO-EVAPORATIVE
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
416.74
45.92
80.09
0.00
0.21
70.27
0.00
613.22
0.00
0.00
613.22
OZONE, mg/mi
MIR
537.66
312.03
381.16
0.00
0.00
43.57
0.00
1274.42
0.00
0.00
1274.42
MOR
334.08
116.96
109.39
0.00
0.00
28.81
0.00
589.24
0.00
0.00
589.24
O3/NMOG, mg/mg
MIR
1.29
6.80
4.76
0.00
0.00
0.62
0.00
2.08
0.00
0.00
2.08
MOR
0.80
2.55
1.37
0.00
0.00
0.41
0.00
0.96
0.00
0.00
0.96
FTP EXHAUST AND EVAPORATIVE SUMMATION
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
471.70
64.92
111.20
1.79
0.27
74.82
4.89
729.59
1439.45
13.69
2182.73
OZONE, mg/mi
MIR
606.09
435.48
538.48
1.16
0.00
46.39
27.39
1654.99
77.73
0.21
1732.92
MOR
375.10
165.84
155.21
0.73
0.00
30.68
8.21
735.76
54.70
0.13
790.59
O3/NMOG, mg/mg
MIR
1.28
6.71
4.84
0.65
0.00
0.62
5.60
2.27
0.05
0.02
0.79
MOR
0.80
2.55
1.40
0.40
0.00
0.41
1.68
1.01
0.04
0.01
0.36
C-4

-------
Ford Taurus, M85 fuel
FTP WTD-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
20.02
5.81
14.66
0.46
0.06
247.75
15.61
304.37
2480.03
24.79
2809.19
OZONE, mg/mi
MIR
24.23
37.07
77.15
0.23
0.00
138.82
109.47
386.96
133.92
0.37
521.26
MOR
14.65
14.88
22.59
0.15
0.00
69.54
32.03
153.84
94.24
0.23
248.31
O3/NMOG, mg/mg
MIR
1.21
6.38
5.26
0.50
0.00
0.56
7.01
1.27
0.05
0.02
0.19
MOR
0.73
2.56
1.54
0.33
0.00
0.28
2.05
0.51
0.04
0.01
0.09
FTP WTO-EVAPORATIVE
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
215.76
12.45
51.17
0.00
0.19
75.34
0.00
354.91
0.00
0.00
354.91
OZONE, mg/mi
MIR
238.08
82.04
268.12
0.00
0.00
42.44
0.00
630.68
0.00
0.00
630.68
MOR
150.76
30.78
77.71
0.00
0.00
21.64
0.00
280.88
0.00
0.00
280.88
O3/NMOG, mg/mg
MIR
1.10
6.59
5.24
0.00
0.00
0.56
0.00
1.78
0.00
0.00
1.78
MOR
0.70
2.47
1.52
0.00
0.00
0.29
0.00
0.79
0.00
0.00
0.79
FTP EXHAUST AND EVAPORATIVE SUMMATION
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
235.78
18.26
65.83
0.46
0.25
323.09
15.61
659.28
2480.03
24.79
3164.10
OZONE, mg/mi
MIR
262.30
119.12
345.27
0.23
0.00
181.26
109.47
1017.65
133.92
0.37
1151.94
MOR
165.42
45.65
100.29
0.15
0.00
91.17
32.03
434.72
94.24
0.23
529.19
O3/NMOG, mg/mg
MIR
1.11
6.52
5.24
0.50
0.00
0.56
7.01
1.54
0.05
0.02
0.36
MOR
0.70
2.50
1.52
0.33
0.00
0.28
2.05
0.66
0.04
0.01
0.17
C-5

-------
Dodge Spirit, RFC fuel
FTP WTO-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
49.00
20.00
35.92
3.01
0.30
2.56
2.37
113.16
2518.30
29.11
2660.58
OZONE, mg/mi
MIR
60.15
139.01
182.87
3.49
0.00
1.59
13.35
400.46
135.99
0.44
536.88
MOR
35.92
55.30
53.36
1.84
0.00
1.05
3.68
151.16
95.70
0.27
247.12
O3/NMOG, mg/mg
MIR
1.23
6.95
5.09
1.16
0.00
0.62
5.64
3.54
0.05
0.02
0.20
MORI
0.73
2.77
1.49
0.61
0.00
0.41
1.56
1.34
0.04
0.01
0.09
FTP WTD-EVAPORATIVE
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
82.01
20.91
46.41
0.00
0.18
11.75
0.00
161.26
0.00
0.00
161.26
OZONE, mg/mi
MIR
100.45
146.24
234.68
0.00
0.00
7.28
0.00
488.65
0.00
0.00
488.65
MOR
61.93
54.99
67.75
0.00
0.00
4.82
0.00
189.49
0.00
0.00
189.49
03/NMOG, mg/mg
MIR
1.22
6.99
5.06
0.00
0.00
0.62
0.00
3.03
0.00
0.00
3.03
MOR
0.76
2.63
1.46
0.00
0.00
0.41
0.00
1.18
0.00
0.00
1.18
FTP EXHAUST and EVAPORATIVE SUMMATION
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
131.01
40.91
82.33
3.01
0.49
14.31
2.37
274.42
2518.30
29.11
2821.83
OZONE, mg/mi
MIR
160.59
285.25
417.55
3.49
0.00
8.87
13.35
889.11
135.99
0.44
1025.54
MOR
97.85
110.30
121.11
1.84
0.00
5.87
3.68
340.64
95.70
0.27
436.61
O3/NMOG, mg/mg
MIR
1.23
6.97
5.07
1.16
0.00
0.62
5.64
3.24
0.05
0.02
0.36
MOR
0.75
2.70
1.47
0.61
0.00
0.41
1.56
1.24
0.04
0.01
0.15
C-6

-------
Dodge Spirit, M85 fuel
FTP WTO-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehvdes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
17.65
4.84
9.52
0.88
0.10
228.01
15.21
276.21
5136.75
23.44
5436.39
OZONE, mg/mi
MIR
21.60
32.33
45.41
0.44
0.00
127.76
106.38
333.92
277.38
0.35
611.66
MOR
13.06
13.21
13.22
0.29
0.00
64.01
30.93
134.72
195.20
0.22
330.14
O3/NMOG, mg/mg
MIR
1.22
6.68
4.77
0.50
0.00
0.56
7.00
1.21
0.05
0.02
0.11
MOR
0.74
2.73
1.39
0.33
0.00
0.28
2.03
0.49
0.04
0.01
0.06
FTP WTD-EVAPORATIVE
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
93.54
9.25
26.36
0.00
0.13
60.27
0.00
189.55
0.00
0.00
189.55
OZONE, mg/mi
MIR
106.82
60.97
129.55
0.00
0.00
34.25
0.00
331.59
0.00
0.00
331.59
MOR
67.19
22.89
37.28
0.00
0.00
17.97
0.00
145.33
0.00
0.00
145.33
O3/NMOG, mg/mg
MIR
1.14
6.59
4.91
0.00
0.00
0.57
0.00
1.75
0.00
0.00
1.75
MOR
0.72
2.47
1.41
0.00
0.00
0.30
0.00
0.77
0.00
0.00
0.77
FTP EXHAUST AND EVAPORATIVE SUMMATION
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
111.20
14.09
35.88
0.88
0.23
288.27
15.21
465.76
5136.75
23.44
5625.95
OZONE, mg/mi
MIR
128.41
93.30
174.96
0.44
0.00
162.02
106.38
665.51
277.38
0.35
943.25
MOR
80.25
36.10
50.50
0.29
0.00
81.98
30.93
280.05
195.20
0.22
475.47
O3/NMOG, mg/mg
MIR
1.15
6.62
4.88
0.50
0.00
0.56
7.00
1.43
0.05
0.02
0.17
MOR
0.72
2.56
1.41
0.33
0.00
0.28
2.03
0.60
0.04
0.01
0.08
C-7

-------
Chevrolet Lumina, RFG fuel
FTP WTD-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
70.00
25.34
33.20
0.80
0.08
6.65
3.56
139.62
1969.43
29.93
2138.99
OZONE, mg/mi
MIR
86.62
183.38
158.79
0.58
0.00
4.12
22.13
455.62
106.35
0.45
562.42
MOR
52.26
73.72
46.19
0.36
0.00
2.72
6.72
181.97
74.84
0.28
257.08
O3/NMOG, mg/mg
MIR
1.24
7.24
4.78
0.73
0.00
0.62
6.22
3.26
0.05
0.02
0.26
MOR
0.75
2.91
1.39
0.45
0.00
0.41
1.89
1.30
0.04
0.01
0.12
FTP WTD-EVAPORATIVE
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
104.05
9.57
48.70
0.00
1.03
18.55
0.00
181.91
0.00
0.00
181.91
OZONE, mg/mi
MIR
129.93
59.18
238.15
0.00
0.00
11.50
0.00
438.77
0.00
0.00
438.77
MOR
79.16
22.25
68.49
0.00
0.00
7.61
0.00
177.51
0.00
0.00
177.51
O3/NMOG, mg/mg
MIR
1.25
6.18
4.89
0.00
0.00
0.62
0.00
2.41
0.00
0.00
2.41
MOR
0.76
2.32
1.41
0.00
0.00
0.41
0.00
0.98
0.00
0.00
0.98
FTP EXHAUST AND EVAPORATIVE SUMMATION
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
174.05
34.91
81.90
0.80
1.12
25.20
3.56
321.53
1969.43
29.93
2320.90
OZONE, mg/mi
MIR
216.55
242.56
396.95
0.58
0.00
15.62
22.13
894.39
106.35
0.45
1001.19
MOR
131.42
95.97
114.68
0.36
0.00
10.33
6.72
359.48
74.84
0.28
434.59
O3/NMOG, mg/mg
MIR
1.24
6.95
4.85
0.73
0.00
0.62
6.22
2.78
0.05
0.02
0.43
MOR
0.76
2.75
1.40
0.45
0.00
0.41
1.89
1.12
0.04
0.01
0.19
C-8

-------
Chevrolet Lumina, E85 fuel
FTP WTD-EXHAUST
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
me/mi
EMISSION
34.50
21.99
13.03
1.45
0.12
149.67
23.62
244.37
3189.70
107.22
3541.29
OZONE mg/mi
MIR
36.69
157.29
58.70
0.72
0.00
199.15
136.34
588.89
172.24
1.61
762.74
MOR
22.38
65.93
17.04
0.48
0.00
108.63
50.51
264.97
121.21
1.00
387.18
O3/NMOG, mg/mg
MIR
1.06
7.15
4.50
0.50
0.00
1.33
5.77
2.41
0.05
0.02
0.22
MOR
0.65
3.00
1.31
0.33
0.00
0.73
2.14
1.08
0.04
0.01
0.11
FTP WTD-EVAPORATTVE
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
50.74
2.48
11.74
0.00
0.14
61.14
0.00
126.23
0.00
0.00
126.23
OZONE, mg/mi
MIR
56.31
15.17
59.52
0.00
0.00
59.55
0.00
190.55
0.00
0.00
190.55
MOR
35.58
5.68
17.19
0.00
0.00
31.96
0.00
90.41
0.00
0.00
90.41
O3/NMOG, mg/mg
MIR
1.11
6.12
5.07
0.00
0.00
0.97
0.00
1.51
0.00
0.00
1.51
MOR
0.70
2.29
1.46
0.00
0.00
0.52
0.00
0.72
0.00
0.00
0.72
FTP EXHAUST AND EVAPORATIVE SUMMATION
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
85.24
24.47
24.77
1.45
0.26
210.81
23.62
370.61
3189.70
107.22
3667.52
OZONE
MIR
93.00
172.45
118.22
0.72
0.00
258.71
136.34
779.44
172.24
1.61
953.29
mg/mi
MOR
57.96
71.60
34.23
0.48
0.00
140.60
50.51
355.38
121.21
1.00
477.59
O3/NMOG, mg/mg
MIR
1.09
7.05
4.77
0.50
0.00
1.23
5.77
2.10
0.05
0.02
0.26
MOR
0.68
2.93
1.38
0.33
0.00
0.67
2.14
0.96
0.04
0.01
0.13
C-9

-------
Dodge Caravan, RFG fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
26.19
6.54
13.30
0.00
0.02
0.00
13.11
59.15
1380.00
19.50
1458.65
OZONE, mg/mi
MIR
32.73
38.80
59.55
0.00
0.00
0.00
67.79
198.87
74.52
0.29
273.68
MOR
19.55
15.33
17.33
0.00
0.00
0.00
16.45
68.65
52.44
0.18
121.28
O3/NMOG, mg/mgl
MIR
1.25
5.94
4.48
0.00
0.00
0.00
5.17
3.36
0.05
0.02
0.19
MOR
0.75
2.35
1.30
0.00
0.00
0.00
1.26
1.16
0.04
0.01
0.08
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
ms/mi
EMISSION
40.43
9.77
28.80
0.00
0.19
0.00
1.80
81.00
3126.67
36.08
3243.74
OZONE, mg/mi
MIR
52.02
58.33
137.73
0.00
0.00
0.00
7.46
255.54
168.84
0.54
424.92
MOR
31.09
23.12
40.17
0.00
0.00
0.00
2.57
96.95
118.81
0.34
216.10
O3/NMOG, mg/mg
MIR
1.29
5.97
4.78
0.00
0.00
0.00
4.14
3.16
0.05
0.02
0.13
MOR
0.77
2.37
1.39
0.00
0.00
0.00
1.43
1.20
0.04
0.01
0.07
COMPOSITE PHASES 1 & 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
28.28
7.01
15.57
0.00
0.04
0.00
11.45
62.35
1635.76
21.93
1720.04
OZONE, mg/mi
MIR
35.55
41.66
71.00
0.00
0.00
0.00
58.95
207.17
88.33
0.33
295.83
MOR
21.24
16.47
20.67
0.00
0.00
0.00
14.42
72.80
62.16
0.20
135.16
O3/NMOG, mg/mg
MIR
1.26
5.94
4.56
0.00
0.00
0.00
5.15
3.32
0.05
0.02
0.17
MOR
0.75
2.35
1.33
0.00
0.00
0.00
1.26
1.17
0.04
0.01
0.08
C-10

-------
Dodge Caravan, CNG fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
1.23
0.11
0.00
0.00
0.00
0.00
3.34
4.67
170.00
44.77
219.44
OZONE, mg/mi
MIR
1.41
0.68
0.00
0.00
0.00
0.00
23.54
25.63
9.18
0.67
35.49
MOR
0.86
0.26
0.00
0.00
0.00
0.00
6.90
8.02
6.46
0.42
14.89
O3/NMOG, mg/mg
MIR
1.15
6.36
0.00
0.00
0.00
0.00
7.06
5.49
0.05
0.02
0.16
MOR
0.70
2.43
0.00
0.00
0.00
0.00
2.07
1.72
0.04
0.01
0.07
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
3.45
1.12
1.18
0.00
0.00
0.00
1.01
6.76
930.00
202.70
1139.47
OZONE, mg/mi
MIR
3.85
7.51
7.93
0.00
0.00
0.00
6.03
25.32
50.22
3.04
78.58
MOR
2.27
3.14
2.42
0.00
0.00
0.00
1.94
9.76
35.34
1.89
46.99
O3/NMOG, mg/mg
MIR
1.12
6.68
6.73
0.00
0.00
0.00
5.97
3.74
0.05
0.02
0.07
MOR
0.66
2.79
2.05
0.00
0.00
0.00
1.92
1.44
0.04
0.01
0.04
COMPOSITE PHASES 1 &2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
1.55
0.26
0.17
0.00
0.00
0.00
2.99
4.98
281.29
67.89
354.15
OZONE, mg/mi
MIR
1.76
1.68
1.16
0.00
0.00
0.00
20.98
25.59
15.19
1.02
41.79
MOR
1.07
0.68
0.35
0.00
0.00
0.00
6.17
8.27
10.69
0.63
19.59
O3/NMOG, mg/mg
MIR
1.14
6.56
6.73
0.00
0.00
0.00
7.01
5.14
0.05
0.02
0.12
MOR
0.69
2.66
2.05
0.00
0.00
0.00
2.06
1.66
0.04
0.01
0.06
C-ll

-------
Ford Taurus, RFG fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
rag/mi
EMISSION
41.90
9.45
20.80
0.00
0.02
17.11
837
97.65
2930.00
17.63
3045.28
OZONE, mg/mi
MIR
5232
61.03
73.79
0.00
0.00
10.61
46.89
244.64
158.22
0.26
403.13
MOR
31.28
24.51
21.38
0.00
0.00
7.02
13.12
97.31
111.34
0.16
208.81
03/NMOG, mg/mg
MIR
1.25
6.46
3.55
0.00
0.00
0.62
5.61
2.51
0.05
0.02
0.13
MOR
0.75
2.59
1.03
0.00
0.00
0.41
1.57
1.00
0.04
0.01
0.07
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
324.99
110.00
275.80
0.00
0.88
0.00
4.00
715.66
49070.00
129.38
49915.04
OZONE, mg/mi
MIR
412.55
725.72
983.76
0.00
0.00
0.00
16.51
2138.54
2649.78
1.94
4790.26
MOR
246.61
288.17
285.25
0.00
0.00
0.00
5.37
825.41
1864.66
1.20
2691.27
O3/NMOG, mg/mg
MIR
1.27
6.60
3.57
0.00
0.00
0.00
4.13
2.99
0.05
0.02
0.10
MOR
0.76
2.62
1.03
0.00
0.00
0.00
1.34
1.15
0.04
0.01
0.05
COMPOSITE PHASES 1 & 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
8335
24.17
58.14
0.00
0.15
14.61
7.73
188.14
9686.21
34.00
990835
OZONE
MIR
105.07
158.36
207.04
0.00
0.00
9.06
42.44
521.96
523.06
0.51
1045.53
mg/mi
MOR
62.81
63.12
60.02
0.00
0.00
5.99
11.99
203.92
368.08
0.32
572.31
O3/NMOG, mg/mg
MIR
1.26
6.55
3.56
0.00
0.00
0.62
5.49
2.77
0.05
0.02
0.11
MOR
0.75
2.61
1.03
0.00
0.00
0.41
1.55
1.08
0.04
0.01
0.06
C-12

-------
Ford Taurus, M85 fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
3.49
0.98
3.49
0.00
0.00
58.63
19.79
86.37
1700.00
6.82
1793.19
OZONE, mg/mi
MIR
4.50
6.53
13.03
0.00
0.00
32.83
137.25
194.15
91.80
0.10
286.05
MOR
2.66
2.62
3.75
0.00
0.00
16.42
40.88
66.33
64.60
0.06
130.99
O3/NMOG, mg/mg
MIR
1.29
6.68
3.73
0.00
0.00
0.56
6.94
2.25
0.05
0.02
0.16
MOR
0.76
2.68
1.08
0.00
0.00
0.28
2.07
0.77
0.04
0.01
0.07
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
70.14
19.81
66.82
0.00
0.06
43.81
2.57
203.22
36695.00
63.44
36961.66
OZONE
MIR
84.99
128.81
199.38
0.00
0.00
24.54
14.29
452.02
1981.53
0.95
2434.50
mg/mi
MOR
51.72
53.31
57.28
0.00
0.00
12.27
4.66
179.23
1394.41
0.59
1574.23
O3/NMOG, mg/mg
MIR
1.21
6.50
2.98
0.00
0.00
0.56
5.57
2.22
0.05
0.02
0.07
MOR
0.74
2.69
0.86
0.00
0.00
0.28
1.82
0.88
0.04
0.01
0.04
COMPOSITE PHASES 1 & 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
13.25
3.74
12.77
0.00
0.01
56.46
17.26
103.48
6824.27
15.11
6942.86
OZONE, mg/mi —1
MIR
16.29
24.44
40.32
0.00
0.00
31.62
119.25
231.91
368.51
0.23
600.64
MOR
9.85
10.04
11.59
0.00
0.00
15.81
35.57
82.86
259.32
0.14
342.32
O3/NMOG, mg/mg
MIR
1.23
6.54
3.16
0.00
0.00
0.56
6.91
2.24
0.05
0.02
0.09
MOR
0.74
2.69
0.91
0.00
0.00
0.28
2.06
0.80
0.04
0.01
0.05
C-13

-------
Dodge Spirit, RFG fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mgftni
EMISSION
21.25
7.56
11.49
0.09
0.00
0.00
17.81
58.19
2550.00
23.50
2631.69
OZONE mg/mi
MIR
27.50
42.50
51.03
0.05
0.00
0.00
98.15
216.55
137.70
0.35
354.61
MOR
16.52
17.10
14.89
0.03
0.00
0.00
26.98
73.94
96.90
0.22
171.05
O3/NMOG, mg/mg
MIR
1.29
5.62
4.44
0.50
0.00
0.00
5.51
3.72
0.05
0.02
0.13
MOR
0.78
2.26
1.30
0.33
0.00
0.00
1.52
1.27
0.04
0.01
0.07
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mf/mi
EMISSION
182.47
197.84
195.71
1.85
0.26
0.00
5.45
583.57
33830.00
180.63
34594.20
OZONE, mg/mi
MIR
210.99
1428.83
784.35
0.92
0.00
0.00
23.33
2448.43
1826.82
2.71
4277.96
MOR
127.64
575.73
226.88
0.61
0.00
0.00
6.98
937.84
1285.54
1.68
2225.06
O3/NMOG, mg/mg
MIR
1.16
7.22
4.01
0.50
0.00
0.00
4.28
4.20
0.05
0.02
0.12
MOR
0.70
2.91
1.16
0.33
0.00
0.00
1.28
1.61
0.04
0.01
0.06
COMPOSITE PHASES 1 & 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mgftni
EMISSION
44.85
35.42
38.46
0.35
0.04
0.00
16.00
135.12
7130.29
46.51
7311.92
OZONE, mg/mi
MIR
54.37
245.50
158.41
0.17
0.00
0.00
87.19
543.36
385.04
0.70
929.10
MOR
32.79
98.90
45.94
0.12
0.00
0.00
24.05
200.44
270.95
0.43
471.82
O3/NMOG, mg/mg
MIR
1.21
6.93
4.12
0.50
0.00
0.00
5.45
4.02
0.05
0.02
0.13
MOR
0.73
2.79
1.19
0.33
0.00
0.00
1.50
1.48
0.04
0.01
0.06
C-14

-------
Dodge Spirit, M85 fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
7.05
4.55
3.19
0.00
0.03
5.09
21.81
41.72
3825.00
12.46
3879.18
OZONE, mg/mi
MIR
8.20
31.86
10.93
0.00
0.00
2.85
144.39
198.23
206.55
0.19
404.97
MOR
5.06
13.46
3.13
0.00
0.00
1.43
42.36
65.44
145.35
0.12
210.90
O3/NMOG, mg/mg
MIR
1.16
7.00
3.42
0.00
0.00
0.56
6.62
4.75
0.05
0.02
0.10
MOR
0.72
2.96
0.98
0.00
0.00
0.28
1.94
1.57
0.04
0.01
0.05
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
AT'natics
\ nes
Unknowns
Alcohols/Ethers
Aldehvdes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
111.41
79.57
74.00
0.00
0.22
62.75
16.46
344.40
63365.00
111.45
63820.85
OZONE, mg/mi
MIR
130.11
562.40
268.71
0.00
0.00
35.14
113.23
1109.59
3421.71
1.67
4532.97
MOR
80.59
232.04
77.63
0.00
0.00
17.57
33.27
441.10
2407.87
1.04
2850.01
O3/NMOG, mg/mg
MIR
1.17
7.07
3.63
0.00
0.00
0.56
6.88
3.22
0.05
0.02
0.07
MOR
0.72
2.92
1.05
0.00
0.00
0.28
2.02
1.28
0.04
0.01
0.04
COMPOSITE PHASES 1 & 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
22.34
15.54
13.56
0.00
0.06
13.53
21.02
86.04
12543.36
26.95
12656.35
OZONE, mg/mi
MIR
26.05
109.54
48.68
0.00
0.00
7.58
139.83
331.68
677.34
0.40
1009.43
MOR
16.12
45.47
14.04
0.00
0.00
3.79
41.03
120.45
476.65
0.25
597.34
O3/NMOG, mg/mg
MIR
1.17
7.05
3.59
0.00
0.00
0.56
6.65
3.85
0.05
0.02
0.08
MOR
0.72
2.93
1.04
0.00
0.00
0.28
1.95
1.40
0.04
0.01
0.05
C-15

-------
Chevrolet Lumina, RFG fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
31.63
9.63
26.32
0.00
0.02
0.00
10.36
77.96
3820.00
22.09
3920.05
OZONE, mg/mi
MIR
38.59
67.56
64.53
0.00
0.00
0.00
60.01
230.68
206.28
0.33
437.29
MOR
23.08
28.01
18.49
0.00
0.00
0.00
18.58
88.16
145.16
0.21
233.53
O3/NMOG, mg/mg
MIR
1.22
7.02
2.45
0.00
0.00
0.00
5.80
2.96
0.05
0.02
0.11
MOR
0.73
2.91
0.70
0.00
0.00
0.00
1.79
1.13
0.04
0.01
0.06
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
486.80
235.79
412.98
0.09
0.41
0.00
2.06
1138.12
85060.00
205.88
86404.00
OZONE, mg/mi
MIR
604.24
1751.26
1301.80
0.83
0.00
0.00
11.00
3669.13
4593.24
3.09
8265.46
MOR
363.25
713.14
372.94
0.33
0.00
0.00
3.62
1453.28
3232.28
1.91
4687.47
O3/NMOG, mg/mg
MIR
1.24
7.43
3.15
9.24
0.00
0.00
5.35
3.22
0.05
0.02
0.10
MOR
0.75
3.02
0.90
3.64
0.00
0.00
1.76
1.28
0.04
0.01
0.05
COMPOSITE PHASES 1 & 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
98.28
42.74
82.94
0.01
0.07
0.00
9.14
233.20
15715.86
49.01
15998.06
OZONE
MIR
121.41
314.10
245.70
0.12
0.00
0.00
52.84
734.17
848.66
0.74
1583.56
mg/mi
MOR
72.89
128.33
70.39
0.05
0.00
0.00
16.39
288.05
597.20
0.46
885.71
O3/NMOG, mg/mg
MIR
1.24
7.35
2.96
9.24
0.00
0.00
5.78
3.15
0.05
0.02
0.10
MOR
0.74
3.00
0.85
3.64
0.00
0.00
1.79
1.24
0.04
0.01
0.06
C-16

-------
Chevrolet Lumina, E85 fuel
REP05 PHASE 1
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
6.38
6.18
3.76
0.00
0.02
1.08
12.43
29.85
3310.00
30.59
3370.44
OZONE, mg/ni
MIR
6.34
44.42
6.29
0.00
0.00
1.45
78.68
137.19
178.74
0.46
316.39
MOR
3.93
19.02
1.80
0.00
0.00
0.79
26.31
51.86
125.78
0.28
177.92
O3/NMOG, mg/mg
MIR
0.99
7.19
1.67
0.00
0.00
1.34
6.33
4.60
0.05
0.02
0.09
MOR
0.62
3.08
0.48
0.00
0.00
0.73
2.12
1.74
0.04
0.01
0.05
REP05 PHASE 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
29.86
102.71
49.67
0.00
0.12
0.62
9.45
192.44
58815.00
166.60
59174.04
OZONE
MIR
37.55
736.08
166.51
0.00
0.00
0.84
52.77
993.73
3176.01
2.50
4172.24
mg/m
MOR
22.37
317.14
48.17
0.00
0.00
0.46
20.47
408.60
2234.97
1.55
2645.12
O3/NMOG, mg/mg
MIR
1.26
7.17
3.35
0.00
0.00
1.34
5.58
5.16
0.05
0.02
0.07
MOR
0.75
3.09
0.97
0.00
0.00
0.73
2.17
2.12
0.04
0.01
0.04
COMPOSITE PHASES 1 & 2
Compound
CLASS
Alkanes
Alkenes
Aromatics
Alkynes
Unknowns
Alcohols/Ethers
Aldehydes/Ketones
TOTAL NMOG
CO
CH4
TOTAL EMISSIONS
mg/mi
EMISSION
9.82
20.31
10.48
0.00
0.03
1.01
11.99
53.66
11437.52
50.50
11541.68
OZONE, mg/na
MIR
10.91
145.70
29.75
0.00
0.00
1.36
74.88
262.61
617.63
0.76
880.99
MOR
6.63
62.68
8.59
0.00
0.00
0.74
25.46
104.09
434.63
0.47
539.19
O3/NMOG, mg/mg
MIR
1.11
7.17
2.84
0.00
0.00
1.34
6.25
4.89
0.05
0.02
0.08
MOR
0.67
3.09
0.82
0.00
0.00
0.73
2.12
1.94
0.04
0.01
0.05
C-17

-------
APPENDIX D: Chamber Initial Conditions, Observed
I2h Reaction Products, and Reactivity Parameters for
Irradiations of Exhaust and/or Surrogate Samples for
          RFG, M85, E85, and CNG Fuels
                      D-l

-------
Table Dl. Initial conditions for photochemical experiments using exhaust from RFG fuel.
Initial parameter
Vehicle
VOC (ppmC)
NOX (ppmv)
VOC/NOX
Total paraffin (%)
Total olefin (%)
Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
Table Dl con't. Initial
Initial parameter
Vehicle
VOC (ppmC)
NOX (ppmv)
VOC/NOX
Total paraffin (%)
Total olefin (%)
Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
IR51 IR52
Caravan Caravan
2 2.51
0.35 0.424
5.72 5.92
44.5 44
17.8 17.4
30.9 31.2
5.7 5.7
4.6 6
1.5 1.6
conditions for photochemical experiments using exhaust from RFG fuel.
IR62 , IR64
Spirit Spirit
2.33 2.21
0.413 0.41
5.65 5.39
40.4 43.8
20.9 18.9
31.3 29.4
4.2 5.7
4.2 1.2
1.8 1.6
IR54
Taurus
2.21
0.401
5.51
46.4
17.4
28.5
6.1
1.2
1.6












                                            D2

-------
Table Dl con't. Initial conditions for photochemical experiments using exhaust from RFG fuel.
Initial parameter IR68 ER69

Vehicle Lumina Lumina
VOC (ppmC) 2.34 2.52
NOX (ppmv) 0.386 0.398
VOC/NOX 6.06 6.33
Total paraffin (%) 44.6 41.9
Total olefin (%) 18.7 21.5
Total aromatic (%) 30.4 30.5
Total oxygenate (%) 5.4 4.9
HCHO (ppbv) 5.8 9.5
CH3CHO(ppbv) 1.6 2.8
IR72
\
Lumina
2.24
0.398
5.62
44.9
18.1
31.5
4.1
11
2.6
Table D2. Reaction products from the photooxidation of RFG emissions.
Concentration at 12 h, ppbv IR51 IR52
Ozone 608 481
PAN 31.1 16.6
HCHO 60.1 50.5
CH3CHO 17.3 18.1
acetone 37.4 31.2
methyl ethyl ketone 5.8 5
glyoxal 5.8 5.1
methyl glyoxal - 4.3
[O3]/[PAN] 19.8 27.7
IR54
471
16.6
45.4
15.4
26.8
2.8
3.8
1.2
28.4
                                            D3

-------
Table D2 con't. Reaction products from the photooxidation of RFG emissions.
Concentration at 1 2 h, ppbv IR62
Ozone 618
PAN 23.6
HCHO 36.4
CH3CHO 13.8
acetone 44.0
methyl ethyl ketone 1 .4
glyoxal 3.6
methyl glyoxal 4.4
[O3]/[PAN] 26.2
IR64
615
20.3
78.4
18.5
40.1
2.4
15.9
7.9
38.8
Table D2 con't. Reaction products from the photooxidation of RFG emissions.
Concentration at 12 h, ppbv IR68 IR69
Ozone 603 664
PAN 17.0 19.1
HCHO 91.8 94.4
CH3CHO 17.3 15.4
acetone 33.7 31.8
methyl ethyl ketone 4.8 0.57
glyoxal 7.5 8.0
methyl glyoxal 5.7 5.6
[O3]/[PAN] 35.4 34.4
IR72
598
18.9
64.1
16.2
22.0
0.62
7.9
5.3
31.7
Table D3. Reactivity parameters for the photooxidation of RFG emissions.
Parameter IR51 IR52
IR54
-d[HO]/dt, ppbv/min                              2.23              1.73              1.99
                                            D4

-------
Parameter
d[NO2]/rft, ppbv/min
d[O3]/dt, ppbv/min
time (NO/NO2 crossover), min
time (NO/O3 crossover), min
(NOx-NOU.min
time, [Cy^, min
[OJ« Ppbv
Table D3 con't. Reactivity parameters for the
Parameter
-d[NO]/dt, ppbv/min
d\NO2]/dt, ppbv/min
d[O3]/dt, ppbv/min
time (NO/NO2 crossover), min
time (NO/O3 crossover), min
(NOx-NOU.min
time, [Cy^, min
[O3]max, ppbv
Table D3 con't. Reactivity parameters for the
Parameter
-d[NO]/rft, ppbv/min
rf[NO2]/dt, ppbv/min
d[O3]/dt, ppbv/min
time (NO/NO2 crossover), min
time (NO/O3 crossover), min
IR51
1.77
1.35
75
153
175
>720
608
IR52
1.82
1.10
120
206
120
>720
481
IR54
1.64
1.04
78
214
225
705
471
photooxidation of RFG emissions.
IR62
2.34
1.83
1.28
54
137
150
720
618









IR64
•2.21
1.81
1.32
108
198
207
>720
615
photooxidation of RFG emissions.
IR68
2.11
1.77
1.21
98
191
IR69
2.43
2.08
1.39
86
166
IR72
2.25
1.87
1.18
103
197
D5

-------
Parameter
(NOx-NO)^, min
time, [03],,^, min
[Climax' ppbv
IR68
204
>720
603
IR69
180
>720
664
IR72
212
>720
598
Table D4. Initial conditions for photochemical experiments using exhaust from M85 fuel.
Initial parameter
Vehicle
VOC (ppmC)
NOX (ppmv)
VOC/NOX
Total paraffin (%)
Total olefm (%)
Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
IR59
Taurus
1.47
0.314
4.69
10.5
4.5
8.2
76.4
39.7
0.66
IR60
Taurus
2.13
0.394
5.39
10.0
4.4
8.6
76.6
68.7
1.8
IR61
Taurus
2.45
0.409
5.99
10.5
3.9
8.0
77.2
72.6
1.1
Table D4 con't. Initial conditions for photochemical experiments using exhaust from M85 fuel.
 Initial parameter                                 IR65                         IR66
 Vehicle                                        Spirit                        Spirit
 VOC(ppmC)                                    1.60                         1.86
 NOX (ppmv)                                    0.298                       0.367
 VOC/NOX                                      5.37                         5.06
 Total paraffin (%)                                 10.3                         9.7
 Total olefm (%)                                   3.0                         3.0
 Total aromatic (%)                                6.5                         6.3
                                             D6

-------
Initial parameter IR65
Total oxygenate (%) 79.4
HCHO (ppbv) 60.7
CH3CHO (ppbv) bdl
IR66
80.1
64.9
0.96
Table D5. Reaction products from the photooxidation of M85 emissions.
Concentration at 12 h, ppbv IR59 IR60
Ozone 166 305
PAN 1.03 2.1
HCHO 40.6 56.3
CH3CHO 3.9 5.9
acetone 1.4 6.5
methyl ethyl ketone 0.7 1.05
glyoxal 1.7 1.7
methyl glyoxal 0.49 0.53
[O3]/[PAN] 161 145
IR61
349
3.2
68.5
5.4
5.3
1.4
2.1
0.77
110
Table D5 con't. Reaction products from the photooxidation of M85 emissions.
Concentration at 12 h, ppbv IR65
Ozone 337
PAN 2.4
HCHO 72.1
CH3CHO 4.5
acetone 2.9
methyl ethyl ketone 1 .3
glyoxal 2.9
methyl glyoxal 2.4
IR66
369
2.3
100
5.7
6.9
1.3
4.2
0.81
D7

-------
Concentration at 12 h, ppbv
[03]/[PAN]
IR65 IR66
139 158
Table D6. Reactivity parameters for the photooxidation of M85 emissions.
Parameter
-rf[NO]/Jt, ppbv/min
rf[NO2]/rft, ppbv/min
d[O3]/di, ppbv/min
time (NO/NO2 crossover), min
time (NO/O3 crossover), min
(NOx-NO),,,^, min
time, [(y^, min
[Oalmax. ppbv
Table D6 con't. Reactivity parameters for the
Parameter
-d[NO]/dt, ppbv/min
d[NO2]/dt, ppbv/min
d[O3]/dt, ppbv/min
time (NO/NO2 crossover), min
time (NO/O3 crossover), min
(NOx-NOU.min
time, [O^^m, min
[0 1 ppbv
IR59 IR60 IR61
2.05 3.22 3.80
1.47 2.55 3.03
0.36 0.47 0.61
84 63 56
275 198 178
300 196 182
>720 >720 >720
166 305 349
photooxidation of M85 emissions.
IR65 IR66
1.90 2.42
1.43 1.94
0.71 1.05
63 98
196 251
210 258
>720 >720
337 369
D8

-------
Table D7. Initial conditions for photochemical experiments using exhaust from E85 fuel.
Initial parameter
Vehicle
VOC (ppmC)
NOX (ppmv)
VOC/NOX
Total paraffin (%)
Total olefin (%)
Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
Table D8. Reaction products
Concentration at 12 h, ppbv
Ozone
PAN
HCHO
CH3CHO
acetone
methyl ethyl ketone
glyoxal
methyl glyoxal
[03]/[PAN]
IR70
Lumina
2.21
0.396
5.58
13.6
13.2
8.1
63.6
15.7
84.1
from the photooxidation of E85 emissions.
IR70
535
21.7
84.8
69.7
9.3
bdl
6.3
0.67
24.6
IR71
Lumina
2.06
0.394
5.23
14.0
11.6'
6.9
66.3
29.7
83.5

IR71
562
27.3
125
66.8
5.8
0.45
6.7
2.5
20.6
                                            D9

-------
 Table D9. Reactivity parameters for the photooxidation of E85 emissions.
Parameter
-rf[NO]/rft, ppbv/min
d[NO2]/dt, ppbv/min
d[O3]/dt, ppbv/min
time (NO/NO2 crossover), min
time (NO/O3 crossover), min
(NCvNOU.min
time, [Oj]^, min
[Osl™*, Ppbv
IR70
2.21
1.81
1.19
104
221
237
>720
535
IR71
2.31
1.92
1.17
93
205
216
>720
562
Table D10. Initial conditions for photochemical experiments using exhaust from CNG.
Initial parameter
Vehicle
VOC (ppmC)
NOX (ppmv)
VOC/NOX
Total paraffin (%)
Total olefin (%)
Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
IR74
Caravan
2.54
0.419
6.05
74.3
25.3
0.4
0.0
19.0
0.62
IR75
Caravan
2.70
0.469
5.75
74.7
25.0
0.2
0.0
18.1
0.38
Table Dl 1.  Reaction products from the photooxidation of CNG emissions.




 Concentration at 12 h, ppbv                         IR74                       IR75




 Ozone                                            112                       137
                                            DIG

-------
Concentration at 12 h, ppbv
PAN
HCHO
CHjCHO
acetone
methyl ethyl ketone
glyoxal
methyl glyoxal
[03]/[PAN]
Table D12. Reactivity parameters for the
Parameter
-rf[NO]/720
112
IR75
1.06
104
10.7
7.3
bdl
6.6
0.34
129

IR75
1.12
76.12
0.72
270
508
495
>720
137
Table Dl 3. Initial conditions for photochemical experiments using RFG Surrogate.
Initial parameter
VOC (ppmC)
NOX (ppmv)
VOC/NOX
Total paraffin (%)
IR53
2.14
0.449
4.77
49.1
IR76
2.14
0.391
5.47
49.1
Dll

-------
Initial parameter
Total olefin (%)
Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
Table D13 con't. Initial conditions
Initial parameter
VOC (ppmC)
NOX (ppmv)
VOC/NOX
Total paraffin (%)
Total olefin (%)
Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
IR53
15.7
27
8.1
-
-
for photochemical experiments using M85 surrogate.
IR56 IR58
2.55 2.35
0.394 0.395
6.48 5.96
18.0 17.1
3.3 3.1
7.0 6.6
71.7 73.2
127
-
IR76
15.7
27
8.1
-
-

IR67
2.36
0.398
5.93
17.8
3.3
6.9
72.0
20.9
-
Table D13 con't. Initial conditions for photochemical experiments using E85 and CNG surrogate
 Initial parameter                                IR77                       IR78
                                               (E85)                       (CNG)
 VOC(ppmC)                                   2.19                       2.11
 NOX (ppmv)                                    0.406                       0.387
 VOC/NOX                                     5.36                       5.49
 Total paraffin (%)                               12.1                       75.5
 Total olefin (%)                                 9.1                        24.5
                                          D12

-------
Initial parameter

Total aromatic (%)
Total oxygenate (%)
HCHO (ppbv)
CH3CHO (ppbv)
Table D14. Reaction products
Concentration at 12 h, ppbv
Ozone
PAN
HCHO
CH3CHO
acetone
methyl ethyl ketone
glyoxal
methyl glyoxal
[03]/[PAN]
IR77
(E85)
5.2
73.6
-
39.2
from the photooxidation of the RFG surrogate.
IR53
220
6.4
29.7
15.3
15.8
2.7
3.8
3.5
34.4
IR78
(CNG)
-
-
6.2
-

IR76
278
7.6
33.5
15.2
15.6
-
4.5
4.6
36.6
Table D14 con't. Reaction products from the photooxidation of the M85 surrogate.
Concentration at 12 h, ppbv
Ozone
PAN
HCHO
CH3CHO
acetone
methyl ethyl ketone
IR56 IR58
29.3 198
0.42 2.0
31.7 62.1
5.3 5.9
4.3 5.3
1.6 2.2
IR67
117
0.97
85.1
6.3
5.6
2.0
D13

-------
 Concentration at 12 h, ppbv                IR56                 IR58              IR67
 glyoxal                                  1.6                   1.4                3.1
 methyl glyoxal                           0.30                 0.77                1.4
 [O3]/[PAN]                              69.8                 99.0                121
Table D14 con't.  Reaction products from the photooxidation of the E85 and CNG surrogate.
Concentration at 12 h, ppbv

Ozone
PAN
HCHO
CH3CHO
acetone
methyl ethyl ketone
glyoxal
methyl glyoxal
[03]/[PAN]
Table D15. Reactivity parameters for the photooxidation
Parameter
-rf[NO]/dt (max), ppbv/min
720
IR78
(CNG)
85.4
0.75
52.1
9.0
5.4
bdl
4.18
0.23
114

IR76
1.47
1.11
0.75
211
344
363
>720
                                            D14

-------
Parameter
[Oslma*. ppbv
Table D15 con't. Reactivity parameters
Parameter
-d\NO]/dt (max), ppbv/min
-d[NO]/720
29.3
IR53
220
of the M85 surrogate.
IR58
2.03
1.33
1.56
0.40
124
297
296
>720
198
IR76
278

IR67
1.31
0.79
0.98
0.46
205
466
440
>720
117
Table D15 con't. Reactivity parameters for the photooxidation of the E85 and CNG surrogate.
Parameter
-rf[NO]/dt, ppbv/min
d[NO2]/rft, ppbv/min
d[O3]/dt, ppbv/min
time (NO/NO2 crossover), min
time (NO/O3 crossover), min
(NOx-NO),^, min
time, [OJ^, min
[Ojl™, Ppbv
IR77
(E85)
1.11
0.82
0.64
234
430
439
>720
193
IR78
(CNG)
0.87
0.36
0.43
295
548
537
>720
85.4
                                            D15

-------
APPENDIX E: Time Resolved Profiles of Chamber O3,
    NO, and NO2 (NOX - NO) Concentrations for
 Irradiations of Exhaust and Surrogate Samples for
          RFG, M85, E85, and CNG Fuels
                     E-l

-------
                  IR51: RFG Irradiation (Caravan)
NO      t(N02),max

    d[NO]/d    T
                             6          8
                           Irradiation Time (h)
                                E-2

-------
                            IR52: RFG Irradiation (Caravan)
   0.6
   0.5
>  0.4

Q.
a.

c
o
0)
o
c
o
   0
   u
   0.1
       d[NO]/dt
                                                                  [03],t=12h

                                                                       T
                                       6          8

                                    Irradiation Time (h)
10
12
14
                                            E-3

-------
IR54 : RFG Irradiation (Taurus)
          6          8
        Irradiation Time (h)
               E-4

-------
                            IR62: RFG Irradiation (Spirit)
   0.6
   0.5
Q.
   0.4
C
o

I03
+-I



I
00.2
   0.1
                                     6          8

                                  Irradiation Time (h)
10
12
14
                                        E-5

-------
                             IR64: RFG Irradiation (Spirit)
  0.7
   0.6 -
   0.5 -
Q.
C
   0.4 -
§03
o
O
   0.2  -
   0.1  -
                                       6           8

                                    Irradiation Time (h)
10
12
14
                                              E-6

-------
IR68: RFG Irradiation (Lumina)
          6         8
       Irradiation Time (h)
             E-7

-------
IR69: RFG Irradiation (Lumina)
          6         8
       Irradiation Time (h)
             E-8

-------
              IR72: RFG Irradiation (Lumina)
         t(NO2),max
d[NO]/dt        •
              468
                      Irradiation Time (h)
                            E-9

-------
IR59: M85 Irradiation (Taurus)
468
        Irradiation Time (h)
              E-10

-------
IR60: M85 Irradiation (Taurus)
          6          8
       Irradiation Time (h)
10
12
14
             E-11

-------
                IR61: M85 Irradiation (Taurus)
d[NO]/dt  t(NO2),max
            *

                           6          8
                        Irradiation Time (h)
                              E-12

-------
IR65: M85 Irradiation (Spirit)
         6          8
      Irradiation Time (h)
            E-13

-------
                  IR66: M85 Irradiation (Spirit)
d[NO]/dt
J              t(NO2),max
                           6          8
                        Irradiation Time (h)
                               E-14

-------
IR70:E85 Irradiation (Lumina)
      mniSTnrflTrtWHTmTfttntr^^
          6          8
       Irradiation Time (h)
             E-15

-------
IR71: E85 Irradiation (Lumina)
          6         8
       Irradiation Time (h)
             E-16

-------
  0.6
                         IR74: CNG Irradiation (Caravan)
  0.5
g  0.4

Q.
a.

c
O
'•5  0.3
CO

-------
IR75: CNG Irradiation (Caravan)
           6          8
        Irradiation Time (h)
             E-18

-------
IR53: RFG Surrogate Irradiation
           6          8
        Irradiation Time (h)

               D-19

-------
IR76: RFG Surrogate Irradiation
                                        [03],t=12h

                              d[03]/dt       f
           6          8
         Irradiation Time (h)

                D-20

-------
                        IR56: M85 Surrogate Irradiation
  0.6
          no added HCHO
  0.5
> 0.4

Q.
C
o
I
°0.
  0.1
       NO
                                                       t(NO,),max
    ,      NO-NO
    Y        x
                                  6         8

                               Irradiation Time (h)
10
12
14
                                      E-21

-------
                IR67: M85 Surrogate Irradiation
initial [HCHO]  = 20 ppbv
                          6         8
                       Irradiation Time (h)

                              E-22

-------
              IR58: M85 Surrogate Irradiation
initial  HCHO  = 127 ppbv
                        6         8
                      Irradiation Time (h)

                            E-23

-------
                        IR77: E85 Surrogate Irradiation
  0.6
          initial [CH3CHO] = 39ppbv
  0.5
        NO
> 0.4


Q.
c
o
<§ °-
   0.1
t(NO,),max
   t    NO-NO    [°°U=12h


                        t   °3
                                   6         8

                                Irradiation Time (h)
              10
12
14
                                       E-24

-------
                           IR78: CNG Surrogate Irradiation
   0.6
   0.5
>  0.4

Q.
a.

c
o
'•5  0.3
OJ
-4—•
C
0)
o


°0.2
   0.1
         NO
d[NO]/dt
                               t(NO,),max
                                                  NO  - NO
                                                     3^  "~
                                                                            d[03]/dt
                                                                         NO:O,CrOv
                                                                             o
                                      6          8

                                   Irradiation Time (h)
                                        10
12
14
                                          E-25

-------
APPENDIX F: Time Resolved Profiles of Chamber PAN
    and Carbonyl Compound Concentrations for
  Irradiations of Exhaust and Surrogate Samples for
          RFC, M85, E85, and CNG Fuels
                      F-l

-------
         IR51: RFG Irradiation (Caravan)
                                                                100
PAN
  468
          Irradiation Time (h)

 HCHO  CH3CHO Acetone   MEK
_B ---- 0. ---- £} ---
Glyxoal  Methyl-gloxal
                                                              14
                        F-2

-------
                            IR52: RFG Irradiation (Caravan)
   50
   40  -
JO
Q.
O.

C
.g
*-•
(0
30 -
   20 -
 C
 o
O
   10 -
                   PAN
  468

          Irradiation Time (h)


HCHO  CH3CHO  Acetone   MEK

       ---O---  --Q	O -
                                                             10
                                                                     12
                                                     Glyxoal  Methyl-gloxal
14
                                            F-3

-------
                          IR54: RFG Irradiation (Taurus)
50
40 -
   30  -
5
*-«



c
o
O
20 -
10 -
                                                                                      50
                PAN
   468

           Irradiation Time (h)


 HCHO   CH3CHO  Acetone    MEK

—•	o-	Q-  -
                                                          10
                                                                        12
                                                        Glyxoal  Methyl-gloxal
                                                                                   -  40
                                                                                      C

                                                                                   30.2
                                                                                      0)
                                                                                      o
-  20 O
                                                                                      O

                                                                                      O
                                                                                      O
                                                                                   -  10
 14
                                         F-4

-------
                            IR62: RFG Irradiation (Spirit)
50
40 -
>

Q.


C
O

"ro
•«-•



c
o
O
30  -
20 -
10  -
                                                                                         100
                                      6           8

                                  Irradiation Time (h)
                                                               10
                                                                        12
                 PAN
                        HCHO  CH3CHO  Acetone

                       — • ---- o
                                                    MEK    Glyxoal  Methyl-gloxal
                                                                                      -  80
                                                                                         C

                                                                                   -  60 .9.
                                                                                         •4—1
                                                                                         03
-  40
                                                                                      -  20
                                                                                          I
                                                                                          0


                                                                                         O

                                                                                         O
                                                                                         X
 14
                                           F-5

-------
50
                           IR64: RFG Irradiation (Spirit)
                                    6          8
                                Irradiation Time (h)
                                   10
12
                PAN
HCHO   CH3CHO  Acetone   MEK   Glyxoal  Methyl-gloxal
14
                                         F-6

-------
                         IR68: RFG Irradiation (Lumina)
50
                PAN
  468
         Irradiation Time (h)
HCHO   CH3CHO Acetone   MEK
                                                        10
               12
Glyxoal  Methyl-gloxal
14
                                        F-7

-------
                            IR69: RFG Irradiation (Lumina)
   50
                                                           100
   40  -
   30  -
C
o
4-1
(0
8 20
c
o
O
   10

    0 »=
                                      68

                                   Irradiation Time (h)
                                             12
                   PAN
HCHO   CH3CHO  Acetone

       ...©.
MEK    Glyxoal  Methyl-gloxal
                                 14
                                           F-8

-------
         IR72: RFG Irradiation (Lumina)
                                                                100
PAN
 468
         Irradiation Time (h)

HCHO   CH3CHO Acetone   MEK
Glyxoal  Methyl-gloxal
	ys .   	
                        F-9

-------
                          IR59: M85 Irradiation (Taurus)
10
                             100
 8
c
g
"ro
•*-•

I
o
O
                                  .-Q
                      _--©-'
                PAN
  468

          Irradiation Time (h)

HCHO  CH3CHO  Acetone   MEK
                                                          10
                12
Glyxoal  Methyl-gloxal
                             80
                                                                                       Q.
                                 c
                             60 .2
                                15
                                                                                   40
                                 (D
                                 O

                                 O
                                O

                                O
                                I
                                O
                                                                                   20
                                                                                    14
                                         F-10

-------
          IR60: M85 Irradiation (Taurus)
                                                                  100
PAN
  468
          Irradiation Time (h)

 HCHO   CH3CHO  Acetone   MEK
—•	0---  ---o	o -
                                                     12
Glyxoal  Methyl-gloxal
                                                               -  80
                                                                      Q.
                                                                      C
                                                               H 60 .9.
                                                                      ro
                                                                      
-------
                             IR61: M85 Irradiation (Taurus)
   10
    8  -
Q.
a.

c
o
'-t->

2
+-•



I
o
O
6
                                       6          8

                                    Irradiation Time (h)
                                                          10
12
                   PAN   HCHO  CH3CHO Acetone   MEK   Glyxoal  Methyl-gloxal
                                                                                  100
                                                                                  80
                                                                                         Q.

                                                                                         Q.
             60 .2
      O


      (0
                                                                                  40
                 1
                 O
                 O

                 O


                 O
                                                                                      20
14
                                            F-12

-------
                                IR65: M85 Irradiation (Spirit)
   10
                                                                                      100
Q.
a.

c
o
'•4-1

2
•*->

0>
o
c
o
O
6
                        ,©--•
                                                           "O-,
                                 •---O-'
                                         6           8

                                     Irradiation Time (h)
                                                            10
                                                12
                    PAN
HCHO  CH3CHO  Acetone

 • ---- 0- ----
                                                 MEK   Glyxoal  Methyl-gloxal
                                                                                          80
                                                                                             Q.
                                                                  C

                                                              60  .2
                                                                                      40
                                                                  C
                                                                  
-------
                               IR66: M85 Irradiation (Spirit)
   10
    8 -
.Q
Q.
a.

c
o
V->

2
•*-•

0)
u
c
o
O
p-
         .-o-----
                       €>
                    PAN
  468

           Irradiation Time (h)


 HCHO   CH3CHO Acetone   MEK

—•	o-	-D--  -
                                                              10
                                                         12
                                         Glyxoal  Methyl-gloxal
                                                                       100
                                                                       80
                                                                                           X>
                                                                                           Q.
      C

  60 .2
     •*-•
      (0
                                                                       40
      I
      o
      O
                                                                                           O
                                                                                        20
14
                                             F-14

-------
                              IR70: E85 Irradiation (Lumina)
   100



    90



    80
    70  -
60 -
.n
Q.
a.

c
'•    50  -
I
O
O
    40  -
    30  -
    20
    10  -
                                                                                   100
                   PAN
                            468

                                    Irradiation Time (h)


                          HCHO  CH3CHO Acetone   MEK

                                 ---©--- ---D	<&-
                                                              10
                                                                     12
                                                     Glyxoal   Methyl-gloxal
                                                                                - 80
                                                                                          Q.
      C
H 60 .2

      75
                                                                                      
-------
              IR71: E85 Irradiation (Lumina)
                        6          8
                     Irradiation Time (h)
10
12
     PAN   HCHO  CH3CHO Acetone   MEK    Glyxoal  Methyl-gloxal
                                                                      200
_-_--•©	©—--.---
14
                             F-16

-------
         IR74: CNG Irradiation (Caravan)
                                                                100
                __-G	O
PAN
  468
          Irradiation Time (h)

 HCHO  CH3CHO Acetone   MEK
—•	©---  ---B	
                                                   12
Glyxoal  Methyl-gloxal
                          14
                        F-17

-------
   IR75: CNG Irradiation (Caravan)
                                                          200
          Irradiation Time (h)
PAN
 HCHO  CH3CHO Acetone   MEK   Glyxoal  Methyl-gloxal
— • ---- o- ---- Q ---
                  F-18

-------
                             IR53: RFG Surrogate Irradiation
   20
   15
£
Q.
 C
 o

'•§ 1°
-«-•

 (D
 O
 C
 o
O
                              40
                                       ,0-	
                                                             -•o-..
                    PAN
  468

          Irradiation Time (h)


HCHO  CH3CHO  Acetone   MEK

       ---0-	-Q	^-
                                                              10
                12
Glyxoal  Methyl-gloxal
                              30
                                                                                          Q.
                                                                                          C

                                                                                          O
                              20
                                 C
                                 o
                                O

                                O


                              10
14
                                            F-19

-------
                            IR76: RFG Surrogate Irradiation
   50
   40
.a
a.

•B 30
c
.0
'•*-•
2
*-*

§ 20
C
o
O
   10
                   PAN
  468

           Irradiation Time (h)


 HCHO  CH3CHO  Acetone   MEK

—•— ---©---  ---R-- -
                                                              10
                12
Glyxoal  Methyl-gloxal
                              40
                                                                                          .a
                                                                                          a.
                                 ro
                                 -*-•



                                 I
                              200
                                                                                          O
14
                                             F-20

-------
                            IR56: M85 Surrogate Irradiation
   10
.n
a.

&  6

c
.o
*•>

5
-»-«


§  4
c
o
O
          no added HCHO
                   PAN
  468

          Irradiation Time (h)


HCHO   CH3CHO  Acetone   MEK
                                                            10
                12
Glyxoal  Methyl-gloxal
                             50
                                                                                    40
                                                                                      &
                                                                                       Q.
                                c

                             30.2


                                2
                               ^->

                                
-------
                            IR67: M85 Surrogate Irradiation
   10
    8  -
Q.
Q.

C
o
'*->

2
*-•



I
o
O
6 -
4 -
          initial [HCHO] = 20 ppbv
                                                                                 100
               PAN
 468

         Irradiation Time (h)


HCHO   CH3CHO  Acetone   MEK

       _-.0-_-  ---pi-- -
                                                            10
                                                                    12
                                                        Glyxoal  Methyl-gloxal
                                                                              -  80
                                                                                        Q.
                                                                                        Q.
                                                                              -  60 .g

                                                                                    "(0
                                                        -  40
                                                                                  -  20
                                                                                     I
                                                                                     O
                                                                                    O

                                                                                    O
                                                                                    X
                                                                                    o
                                                                               14
                                            F-22

-------
                            IR58: M85 Surrogate Irradiation
   10
                                                                                200
    8  -
.a
a.
c
g

I
••-•


I
o
O
4 -
    2 -
          initial [HCHO] = 127 ppbv
                   PAN
             6          8

          Irradiation Time (h)


 HCHO  CH3CHO Acetone   MEK

—•— ---©---  ---R--  -O-
                                                                      12
                                                    Glyxoal  Methyl-gloxal
                                                                                       O
                                                                              14
                                           F-23

-------
a.
a.

c
o
'<4->

2
+-•

0)
o
c
o
O
100




 90




 80




 70




 60




 50




 40




 30




 20




 10
                             IR77: E85 Surrogate Irradiation
            initial [CH3CHO] = 39 ppbv
                                               ----o-
                                       6          8

                                    Irradiation Time (h)
                                                          10
12
                   PAN    HCHO   CH3CHO  Acetone   MEK   Glyxoal  Methyl-gloxal
                                                                                     100
                                                                                     80
                                                                                         Q.
                 C

             60 .2
                4-1
                 (0
                 0)
                 o
                 c
                 o
                O
  40
                                                                                         O
                                                                                     20
14
                                            F-24

-------
        IR78: CNG Surrogate Irradiation
                                                             100
             _ _ _ _ . _Q	Q-	0-	
                  6         8
               Irradiation Time (h)
                                           12
PAN
 HCHO  CH3CHO  Acetone   MEK   Glyxoal  Methyl-gloxal
—•	©-—e-  --o-—*--   -
14
                       F-25

-------