EPA/AA/CTAB/PA/82-8
                         Summary of Status of
                     EPA Office  of  Mobile  Sources
                       Characterization Projects
                           as  of March,  1982
                           Thomas M. Baines
                             October,  1982

Technical  Reports   do   not  necessarily  represent   final  EPA
decisions or positions.   They are intended  to  present technical
analysis  of  issues  using  data  which  are   currently  available.
The purpose in  the  release  of such reports  is  to facilitate the
exchange  of  technical information  and to inform the public  of
technical developments which may form the basis  for  a final EPA
decision, position or regulatory action.
      Control Technology Assessment and Characterization Branch
                Emission Control Technology Division
                      Office of Mobile Sources
                 Office of Air, Noise and Radiation
                U.S. Environmental Protection Agency
                         2565 Plymouth Road
                     Ann Arbor, Michigan  48105

-------
                                    -2r-
                              Table  of  Contents


      SECTION                                                     PAGE

I.     Overview and Background  	        4

II.   Summary and Conclusions	.  .        7

III.   Characterization Results

      A. Fuels Work
         1.    Alternate Fuels
              a.   LD Diesel - Project  complete, summary
                   given	       10

              b.   HD Diesel - Project  planned and funded
                   but not started	       26

         2.    Methanol

              a.   LD Vehicles -  Project partially complete,
                   summary of available results  given  ...       27

              b.   M.A.N.  Methanol Engine - Project
                   just starting	       36

      B. Diesel Engine Characterization

         1.    Malfunction  Conditions -  HD Diesel -
              Summary of DDAD 6V-71  results	        38

-------
         2.   Normal Operating Conditions - Status given .  .        51






      C. Aldehydes Emissions at High Mileage -






         1.   Summary of Data	      51






V.    References	    57






VI.   List of Recent CTAB Characterization Reports	    58

-------
                                      -4-

I.    Overview and Background

The  Pollutant  Assessment Program  of  the  EPA  Office  of  Mobile Source  Air
Pollution  Control  (OMSAPC)*  has   focused  on  expanding  the  knowledge  of
pollutants as  they  are emitted from  various  mobile sources.  This  work has
been  done  within OMSAPC, by in-house and  extramural programs,  as well  as
monitoring  the  characterization  efforts  performed by  other  organizations
both within EPA and by industry and  others.   Some of the  principal guiding
objectives of  the OMSAPC Pollutant Assessment  program can  be  summarized  by
the following points.

1.    The  characterization  of pollutants  not normally  tested  and  that  may
      represent a human health concern.

      Currently, and in the  past, a large  amount  of effort has  been expended
      by  industry and  EPA   characterizing  the  hydrocarbon,  carbon  monoxide
      and  oxides  of  nitrogen  emissions   from  a variety  of  engines  and
      vehicles.   However,  there  may  be  other  compounds  being emitted  by
      vehicles  that may  be  of  concern.   Especially  of  interest  would  be
      those  compounds  that  may  have  a deleterious effect  on  human health.
      Some  of  these  compounds  would be   emitted in varying  amounts  from
      uncontrolled  as  well  as controlled engines.  Other  compounds  (such  as
      catalyst  attrition products)  could  be emitted  mostly   from  vehicles
      which  have emission  control  systems designed  to  control  HC,  CO  and
      NOx.  Various  systems  to improve both emissions  and fuel  economy could
      have  a large  impact   on  unregulated emissions.   Since motor vehicle
      technology  is  evolving in response to  the  need  for improved emissions
      and  fuel  economy,  it   is critical that  OMSAPC characterize new systems
      for  unregulated  pollutants.   Consequently,  the OMSAPC  program  has been
      focused  on characterizing  a  broad  range of  compounds  from present and
      future engine and vehicle technologies.
    The  Office of Mobile  Source  Air Pollution Control  (OMSAPC) is  now the
    Office  of  Mobile Sources  (QMS)  as  a  result  of a  recent  organizational
    change  in EPA.

-------
                                      -5-

2.  Testing for a variety of pollutants under malfunction conditions.

    Much,  if  not  most,   of   the  testing  performed  by   EPA  and  other
    laboratories  has  been done   with  vehicles  and  engines   tuned  to
    manufacturers' recommended  specifications.   However, many  vehicles that
    are in use  today  operate under conditions of  tune  that  do not  meet the
    manufacturers'  recommended  specifications.   This   could   result  in
    increased  emissions  of a  variety  of  both  regulated  and  unregulated
    pollutants, some  of  which  could have negative human health effects.  As
    a  consequence,  OMSAPC  has  tested  a  variety of  engines/vehicles  for
    pollutants  of  concern   under   malfunction   conditions  to  estimate  the
    impact  that such  vehicles/conditions  would have  on  the  environmental
    loading of pollutants.

3.  Fuel parameters.

    Fuel properties can  affect  emissions.   The  trends in Diesel fuel quality
    over the  past decade are generally in the  direction of  poorer  emission
    performance.  Therefore,  the  relationship   between  fuel parameters and
    emissions has been, and continues to be, an area of importance.

    The  future  fuel situation  in  the United States  is somewhat  unclear  in
    that  we  are considering   the  development   of a variety  of  alternate
    sources  of fuel  to supplement conventional  petroleum  sources.   These
    alternate sources  include  lower grade petroleum  crudes,  alternative and
    synthetic fuels derived from coal and  oil  shale  and fuels  derived from
    biomass.   These alternate  source fuels  may have a  dramatic effect  on
    emissions  and,  as such, OMSAPC has  performed some characterization  on
    these  emissions  as  well as remained  abreast  of the  field  in  general.
    Also,  some  testing has  been done  on  emissions from Diesel  vehicles,  as
    these  emissions  may be  impacted  by  fuel parameters.   This  effort will
    continue  in an  attempt to more  fully  characterize  the  future  fuels.
    This work is of importance  in  that it helps assure  that  alternate fuels
    are   environmentally   acceptable.    One   can   probably   tailor   fuel

-------
                                     -6-

    composition  and   processes  to   obtain   the   maximum   cost-effective
    environmental  benefit  from  these  fuels  if  one  does  this  sort  of
    characterization before these fuels are widely produced.

4.  Characterization of  pollutants  from engines/vehicles  that are  involved
    in a transition environment.

    There  are  many engines/vehicles   that  are  involved  in  a  transition
    environment  created  by various  market  forces,  regulatory  initiatives,
    fuel economy incentives,  etc.  OMSAPC is  very  interested in  character-
    izing  the  emissions  from these vehicles/engines  to be able to  evaluate
    the impact  that this transition may have.  For example,  the  heavy-duty
    engine manufacturers  have now currently changed most  of their  engines
    from the  traditional,  naturally  aspirated type over to  the  turbocharged
    type.  Also,  there is  currently  a trend  towards  Dieselization  of  both
    the light-duty  fleet as well  as  the mid-range heavy-duty fleet.   Compar-
    ative  application  engines  for both of these  fleets have  been tested  so
    that  an  estimate  can  be  made  of how  such  a  change will  impact  the
    environmental  loading  of  pollutants.   Also,  a  variety  of  other  tech-
    nologies  have  been  evaluated   so that  their  influence  can  also  be
    estimated.

With these four broad  objectives  in mind,  a  variety  of  programs  and  projects
have been  performed.   The  more recent  and more important  of  these  projects
are summarized  in  the  following section.   The  purpose  of  this report is  to
provide a  discussion of the characterization results obtained since  the  last
summary report  on  this program (1)* was written  in  August,  1981.  The  data
in this report are  those available from May,  1981  to March, 1982.
*  Number  in  parentheses  represent references  found  in Section  V  titled
"References".

-------
                                     -7-

II. Summary and Conclusions

EPA-OMSAPC is  conducting  a thorough assessment of regulated  and  unregulated
emissions from a  variety of current and  prototype engines.   Extensive  work
is also underway  investigating  the influence of various  fuels on light-duty
vehicle and heavy-duty engine emissions*  This  latter  work includes  projects
on alternate  fuels  such as methanol as well as  fuels derived from  coal  or
oil  shale.   The  following summarizes  the  status   of  the  work  in  this
pollutant assessment area as well as some of the more important findings.

1.  Eight fuels  from synthetic feedstocks  were run in  a light  duty Diesel
    vehicle (Volkswagen)  and the  resultant  emissions were compared  to those
    from  the  vehicle operated  on  a  Diesel  fuel  #2  (DF2)  base  fuel.   The
    synthetic  fuels  tested were:  1) a  Diesel # 2 Marine  fuel processed  from
    shale oil,  2) a Paraho JP-5, 3)  a blend representing a  combination  of
    shale  oil, coal-derived,  and  petroleum  liquids  designated   "Coal  Case
    5A",  4) a 35% (volume) blend of SRC-II (Solvent Refined  Coal)  and  DF2,
    5)  a  blend  representing  the  same  liquids as   number   3),  designated
    "Broadcut  Mid-Continent", 6)  a  25%  (volume) of  EDS (Exxon Donor Solvent)
    with DF2,  and 7) a 25% blend of EDS Naptha with DF2.

    The results of  this work showed that HC, CO and NOx generally increased
    with  the  use  of  the synthetic fuels tested.  The greatest increases  came
    with  the use   of  coal   liquid   blends.   Particulate   emissions  were
    generally somewhat higher  over the FTP with the alternate fuels, except
    for the "Broadcut" fuel which resulted  in lower emissions.  Smoke levels
    were  generally  higher also with  the alternate  fuels,  with  coal liquid
    blends giving the largest increases.   Aldehydes  were little  changed  or
    decreased with  the alternate fuels and  the  same was  true  of  phenols.
    The only  exception was a large  increase in  phenol  emissions with the use
    of  the  25% EDS/DF2  blend.   The Ames  test bioassay data  showed  that for
    almost  all   strains,   the  revertants   per microgram  of  extract   and
    revertants  per  kilometer  were  always  higher   for   the   synthetic  fuel
    emissions  than  from  the base DF2.   The  only exception  to this  is the
    Paraho JP-5 fuel which occasionally resulted in lower values.

-------
                                 -8-

Comparison of  the results  of  this work  with previous  fuels  variables
work shows few consistent trends.  However,  many of the alternate fuels
tested  had  higher aromatics  levels and  lower  cetane  levels  than  the
base fuel.   Previous  work has  shown  that this  could result  in higher
emissions  of  some  pollutants.   The  same  trend  occurred  with  the
alternate fuels emissions.

A  project studying the effects  of  alternate  fuels  on  emissions  from
heavy  duty  Diesel  engines  has  been  planned  and  funded.   The  fuels
studied will be  selected  from  the following:  DF2 (for comparison),  SRC
II/DF2  blend,  EDS/DF2 blend,  DF2 Marine  (Shale),  DF2/used  lubricating
oil blend and  possibly a vegetable oil.   The engine  (Mack  EM6-300)  is
at Southwest Research Institute (SwRI) and  ready  for  testing.   Testing
has been  delayed due  to  higher  priority M.A.N. methanol engine work,
but will  proceed upon completion of the M.A.N. engine testing program.

The testing  of  light  duty vehicles using gasoline  (for  a baseline com-
parison)  and 100% methanol as  the fuels is nearly complete  and about
70% of  the data  are reported.   Much of  the  program went well,  but there
were  several problems.   For  example,  the  emission  results   from  the
Escort  were  not as  repeatable from test to test  as were  the results
from  the  VW.   Also,   the promoted base  metal  catalyst  used   for  the
Escort  running   on methanol was  larger  than  the noble  metal  catalyst
that was  used when  testing the  vehicle  in  its stock  condition.   The
Escort  vehicle  designed  for  methanol developed  carburetor  corrosion
problems  because  it  was   not  equipped   with  a  methanol-protected
carburetor.  Also, W.R. Grace  sent a  promoted base metal catalyst using
a  foam  substrate (usually used for prototype  Diesel  particulate traps)
for use with the VW  and  this  catalyst slowly  disintegrated during  the
testing.   Subsequent   testing  was  done  with  the  promoted  base  metal
catalyst  used  for the Escort.   Some of the  data from  these tests  with
the methanol-fueled VW may  still  be valid but some  (e.g.  the  foam sub-
strate  promoted  base metal catalyst data)  will be difficult to analyze.

-------
                                     -9-

     Tentative conclusions that can be reached at this time from  the  program
     are that vehicles  can be set up  such that they  come close to  meeting
     the levels of the emission standards at low mileage for EC,  CO,  and  NOx
     with  an attendant  decrease  in  particulate  emissions  and  individual
     hydrocarbons.   However,   we  generally  see an  increase  in methanol
     emissions as well as aldehydes and ketones.  The use  of a promoted base
     metal  catalyst   and methanol  as  a  fuel  resulted  in  low  emissions.
     However, the most complete data are  from the  Escort, and  the  fact that
     the promoted base metal catalyst was  twice  the size of the  noble metal
     catalyst makes  a one-to-one  comparison  tricky.  Also, W.R. Grace  has
     not provided  us with  the composition or amount  of active  ingredients
     for the Davex 908 promoted base metal catalyst.  There appears  to be  a
     slight  increase  in  the level of  cyanide and cyanogen with  the use  of
     the promoted base metal catalyst.   This  is  something that will  have to
     be investigated further.

4.   The M.A.N. methanol heavy duty engine  is now being  tested after  several
     delays  due  to  shipping  problems,   dynamometer equipment  failure  and
     engine  ignition  failures.  These  problems  have been corrected and data
     are being generated.  A more complete  report of the  data  will  be avail-
     able later.

5.   A  DDAD  6V-71N  bus  engine   was  tested  in  a  baseline   configuration
     followed  by a  malfunction condition.   The malfunction  condition  was
     representative of a "smoky  bus",  yet was not  so-severe   that  the  "bus"
     would  have been  withdrawn from  service.  Hot  start  transient  tests
     showed  increases in  HC,  CO,  NOx,  particulate  and  smoke.   Composite
     transient  and  modal testing  showed  increases   for  CO,  particulate  and
     smoke, but some reduction in  HC and  NOx.  Aldehydes  were  also increased
     from  the  engine  operating in  the malfunction condition.    The  Ames bio-
     assay  data  showed  no discernible  difference between  the  two con-
     figurations on a revertant per brake  horsepower-hour  basis or  revertant
     per microgram of extract basis.

-------
                                       -10-
6.   Ten  light  duty  gasoline  vehicles  that had  been  driven  approximately
     50,000 miles were  tested  for regulated and unregulated  emissions (with
     special emphasis on aldehydes)  and the results  compared  to low mileage
     vehicles.  The  results  indicated that after 50,000 miles,  the vehicles
     tested emitted  substantially more  HC,  CO,  and  particulate  (increases by
     factors of 3,  2.6,  and 4  respectively).   The  increase in  aldehydes at
     higher mileages was not as large  (about 2  mg/km  at low mileage to about
     4 mg/km at high mileage)  showing that aldehydes  are  well  controlled at
     high mileages  with  catalyst-equipped vehicles compared  to  non-catalyst
     equipped vehicles (which emit about 40 mg/km aldehydes).

     There was  no significant change  in the level  of emissions  of organic
     suIfides,  organic  amines,  ammonia,  cyanide  and  cyanogen,  hydrogen
     sulfide and nitrous oxide.

III. Characterization Results

A.   Fuels Work

1.   Alternative Fuels

     a.          Light-Duty Diesels

OMSAPC's first synthetic fuels emissions evaluation program  (2)  has recently
been completed and  the  final  report  is in preparation.  The major objective
of this project was  to study the  effects  of  available alternate-source fuels
on exhaust emissions from one Diesel vehicle, a 1980  Volkswagen  Rabbit.   The
vehicle was operated  on  a  chassis dynamometer  following two transient  driv-
ing  cycles  (FTP  and  HFET),   and periodically,  several  steady-state  con-
ditions.   Nine fuels were  tested.   Table 1 lists some of  the properties  of
the fuels used.   Some of the  test fuels were blends  of a  base No.  2  Diesel
fuel and alternate-source materials while  others were fuels formulated in  a
study  dealing  with  refinery modeling  for  alternative  fuels.   This  latter
study was conducted by the Department  of Fuels  and Lubricants Technology  of
Southwest Research Institute.

-------
                                     -11-

One  of  the  major challenges  in  performing  this  work was  acquisition  of
sufficient quantities  of  "state-of-the-art" alternate-source materials.   In
most  cases,  these materials  were  still  in  the  laboratory  in pilot  plant
phases of  production.   "First-generation"  liquids can be described  as  those
which have only  been made liquid from the  solid  coal or shale.   No further
processing  would  have  been  done   on  such   liquids.    First-generation
coal-derived  liquids from two  processes  (Solvent  Refined  Coal,  or SRC-II,
and Exxon Donor  Solvent, or EDS)  were  available  in sufficient quantities for
testing and  these  were therefore used in this program.   "Second-generation"
liquids  can  be  described  as  those  which  have  undergone   some  additional
processing after their "first-generation"  processing.   Such processing  may
include hydrotreating,  reforming, etc.  The  only  second-generation liquids
available in sufficient quantities for testing were shale liquids.

-------
TABLE  1   FUEL PROPERTIES AND COMPOSITION

Substance
Fuel Code (EM-
Cetane No. (D613)
Cetane Index (0976)
Gravity, "API 9 60*F
Density, g/ml 9 60*F
Carbon, wt. »
Hydrogen, wt. %
Nitrogen, ppm loxid. pyrolysia)
Sulfur (lamp), I
Calculated II/C, numeric
Carbon No. range (G.C.)
Aromatics, vol. »
Oleflns, vol. % (D1319)
Paraffins, vol. \
Viscosity, cs 9100 °F (D44S)
Gum, riKi/100 ml (0481)
Total solids, mg/f
Metals in fuel, x-ray
Doiling Range, *C (IBP-EP, DU6)
lot point
201 point
301 point
401 point
SOI point
60% point
70t point
BOi point
90t point
95l point
r.usicluo, wt. % (DO&)


Base
DF-2
329-F
SO
52
37.5
O.S37
65.8
13.0
48
0.24
1.81
e-24
21.3
1.7
77.0
2.36
14.3
7.4
0"
101-340
219
231
242
251
2C.O
269
270
290
307
323
1.3
ppm Pb; <100 |

Shale Diesel
Marine
453-F
49
56
37.9
0.835
86.1
13.4
5

-------
TABLE 1 (Cont'd).  FUEL PROPERTIES AND COMPOSITION

Substance
Fuel Code (EM-
Boiling &an9e( *C (IUP-EP, D2887)
10* point
20% point
301 point
40% point
SOI point
COt point
70t point
BOt point
90% point
95* point

Com|>osi tion. Volume t
Kerosene
Petroleum
JP-S
JP-8
Diesel
Petroleum
Shale DFM
Co.il SHC- 1 1
Light Cycle Oil
LSK Naptha
HSR Petroleum
Shale
Coal (Simulated)
H-uut.inu
"'•10 |.|im of Or, Ke, Ni, Cu, Zn, un.l t
Base
DF-2
329-F
104-387
197
220
239
256
2GB
280
292
307
330
347
0.0


0.0
0.0
0.0

100.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
U.O
!g; <70 ppm Pb;
Shale Dleaol
Marine
453-F
118-341
216
2J7
254
26S
274
285
297
307
319
325
0.0


0.0
0.0
0.0

0.0
100.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
<100 i>pm Al and
Parana
JP-5
473-F
157-286
175
187
195
201
210
216
224
234
244
254
0 .0


0.0
100.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Si
Coal Case
5*
474-F
140-416
217
238
254
264
271
284
299
315
344
367
0 .0


17.3
0.0
0.0

66.7
n.o
16.0
0.0
0.0
0.0
0.0
0.0
0.0

35%
SRC-II
47S-P
103-346
"158
178
196
207
219
229
240
255
278
295
0.0


0.0
0.0
0.0

65.0
0.0
35.0
0.0
0.0
0.0
0.0
0.0
0.0

Broadcut
Mid-Continent
476-F
24-399
68
123
155
196
233
251
262
280
314
342
0.0


22.0
0.0
0.0

23.0
0.0
6.2
5.2
7.4
4.8
20.9
0.0
10.5

25%
•SRC-II
478-F
129-508
193
214
232
248
259
271
285
302
321
345
0.0



0.0
0.0
0.0

75.0
0.0
25.0
0.0
0.0
0.0
0.0
n.o
O.I)

25%
• EDS
482-F
128-419
192
210
228
243
257
273
289
305
332
356
0 0



0.0
0.0.
0.0

75.0
0.0
25.0
0.0
0.0
0.0
0.0
n.o
o.o

• 25% EDS
Naphtha
4B5-F
72-455
139
174
197
225
249
264
279
298
314
336
0.0



0.0
0.0
0.0

75.0
0.0
25.0
0.0
0.0
0.0
0.0
o.o
0.0


-------
                                     -14-

The  first-generation  coal-derived liquids  exhibited  boiling ranges  similar
to petroleum-based Diesel fuels.  They  could  not be used by  themselves  in a
Diesel engine due in  part to  their  low cetane number of 25  or  less.   Blends
with  petroleum-based  Diesel  fuel were  used  to  raise  the  cetane level  to
above 35.

The  second-generation shale  oil liquids exhibited boiling ranges  similar  to
petroleum-based  Diesel  fuels  and  had  cetane  numbers  greater  than  44.
Vehicle  operation  with  these  fuels   was  good,   based   on  a  subjective
evaluation.

The  "3-bag" composite FTP values  for HC, CO,  and NOx are shown as bargraphs
in  Figure  1.   The greatest  HC and CO  increases,  as  compared  with the  base
fuel, were observed with the  Broadcut and the 25% SRC-II blend.  Hydrocarbon
emissions  with  these  two  fuels more  than  doubled as  compared to the  base
fuel  and slight  NOx  increases were  seen with all the test  fuels.   Coal  Case
5A  resulted  in slightly more NOx emissions than  the  other blends.   Of the
two middle-distillate coal-derived fuel blends  (25%  SRC-II  and  25% EDS), the
SRC-II  blend was  associated  with  higher  emissions.   The  25% EDS  middle-
distillate  and  the 25%  EDS  naphtha  gave almost identical  HC, CO,  and NOx
emissions.

-------
1.25
1.00
0.75
0.50
0.25
        HC =

                                                                Broadcut
Para'no
 JP-5
                          Shale
                          Diesel
                          Marine
Coal
Case
 5A

  II
  vm
                                                                               25*
                                                                             SRC-II
                                                                                 ii
           Base
           DF-2
                                                         25%
                                                         EDS
                                                          Ii
                           Figqre  1.  Regulated gaseous emissions during FTP  (composite)
  25%
  EDS
Nahptha

                                                                                                                     Ln
                                                                                                                     i

-------
                                     -16-

Fuel consumption results for the test  fuels  during  both transient cycles are
shown  graphically  in  Figure  2.   During  both  cycles,  all  the  test  blends
showed slightly increased  fuel  consumption except Coal Case 5A and  25% EDS.
The 25% EDS appears to result in the same  or slightly lower fuel consumption
as  compared  with the  base fuel.  Coal  Case 5A  showed increased fuel con-
sumption compared with the base fuel during  the HFET,  but  was  about  the same
during the FTP.

Concentrations of a number of individual  low-molecular weight  aldehydes were
determined in CVS-diluted exhaust.   "Total" aldehydes  refer  to the  sum of
the individual aldehyde  emissions.   This  "total"  for each  of  the test fuels
is  shown  graphically  in  Figure  3.   The  "total"  phenols are also  shown
graphically in Figure 3.

"Total"  aldehyde  emission decreases,  as  compared  with the base  fuel, were
observed with the 25%  SRC-II and  the 25% EDS blends.   Both fuel blends gave
similar aldehyde emissions (  3  tng/km).  No  aldehyde  increases  over  the base
fuel  were seen  with  the  fuels  tested  during  the  FTP.    Paraho JP-5  and
Broadcut test fuel were  associated with decreases in FTP phenol emissions as
compared  to  base fuel.  The  25%  EDS blend  roughly doubled the emission of
phenols  during  the FTP  compared to  those  from  the base   fuel.    It  is
interesting to note  that although the aldehyde emissions  for  the 25%  SRC-II
and 25% EDS blend were approximately the  same, the 25%  SRC-II  blend  did not
increase phenols as did  the 25% EDS blend.

      Visible smoke was  measured using an EPA-type smokemeter  over the first
505  seconds  (the  "cold  transient  phase")  of  the  FTP.    The  results  are
summarized in Table 2.

-------
                                                      Base DF-2
                                                      Shale Diesel Marine
                                                      Paraho JP-5
                                                      Coal Case 5A
                                                      Broadcut
                                                      25% SRC-II
                                                      25% EDS
                                                      25% EDS Naphtha
                                                        HFET
I'Jgure 2.   Fuel consumption during FTP and HFET.

-------
  20
   15
oo
e
M
a
o


3 10
•H
   0
          "Total"

         Aldehydes =



          "Total"

          Phenols
           Base DF-2
oo
                  Figure  3..  "Total" aldehyde  and  phenol  emissions during  FTP.

-------
                                     -19-
                   Table  2.   Summary  of Visible  Smoke  Data
Condition
Cold Start peak
                            Smoke Opacity, %, by fuel
                      Base  Shale Paraho Coal   Broad- 35%     25%    25%
                      DF2   DFM   JP-5   5A     cut    SRC-II  SRC-II EDS
21.2  46.8  36.0   66.0   33.0   66.0    58.8   58.2
Cold idle, avg.
(after start)
0.2    1.0   1.4    0.4    3.0   60.0     3.5   4.0
1st accel.
peak
28.2  44.2  61.5   40.5   44.2   92.0    63.5  67.8
Idle at 125 sees,
avg.
0.7    0.5   0.8    0.6    0.5   21.0     1.0   1.7
Accel at 164 sees,
peak
37.5  27.2  20.0   71.2   20.6   59.0    42.0  41.3

-------
                                     -20-

These  data  indicate  rather  dramatic  smoke  effects  when  running the  35%
SRC-II blend.  Its smoke  levels  were  very high at the start and  even  at the
125 second idle, by which time the  emissions  from all the other fuels  showed
very little  smoke.   Because of  such  high smoke and  particulate  levels,  the
testing with 35%  SRC-II was stopped.   The  fuel was then  reblended with 25%
SRC-II and a full set of runs performed.

At idle,  the base  fuel  generally exhibited the lowest smoke levels.  At the
164  second  acceleration,  however,  several  fuels  did  give  lower  smoke
readings  than the  base fuel.   Shale  Diesel  marine, Paraho  JP-5, and  the
Broadcut  all showed lower  smoke  at the 164 second  acceleration than did the
base fuel.   With  the exception  of  the  35% SRC-II, the  greatest  smoke level
increases  were generally  associated  with  the other  test  fuels  containing
coal-derived liquids; Coal Case  5A, 25% SRC-II, and 25% EDS.

The FTP and  HFET  particulate  mass emission results are presented graphically
in  Figure 4.   The trends  by fuel are  similar  for  both  operating  cycles
except  for the 25% SRC-II.   The 25%  SRC-II  particulate  emissions  were 56%
above those  from the base fuel during  the FTP,  but about the same during the
                                                                            v
HFET.   One  possibility  is  that  the  combustion of   the  SRC-II  material
improves  as  the vehicle warms up.  Particulate mass emissions increases were
observed  with  the Coal  Case 5A,  and to  a  lesser extent with  the EDS  blends.

The  BaP  results  are presented  graphically in  Figure  5.   The  largest  BaP
emissions were associated with  the Coal  Case  5A fuel (about  3 times  higher
than for  the base fuel).  Values up  to twice the base  fuel level  were seen
with  the  Shale   Diesel,   Paraho  JP-5,   Broadcut,  and  25%  EDS.   Slight
reductions were observed  with the 25%  EDS  Naptha  and 25% SRC-II.   Comparing
the  25% EDS middle  distillate with  the  25%  SRC-II  shows that the 25%  EDS
produced  twice the BaP associated  with the 25% SRC-II.   However,  a lighter
cut  (i.e.  lower  boiling  range)   of   the  EDS  material,  25%  EDS  naphtha,
resulted  in  approximately the same  BaP  emissions as the 25%  SRC-II.

-------
   0.5
   0.4
   0.3
o
•H
CO
CO
   0.2
   0.1
                                                                 A = Base DP-2
  K = Droadcut
                                                                 B = Shale diesel marine  F  =  25^ SRC-II
                                                                 C = Paraho JP-5


                                                                 D = Coal Case 5A
  G = 25'i HIV5


  II = 25!:. liDS  naphtna
                                 FTP
HFET
                         Figure 4.   Particulate mass emissions during FTP and HFET  cycles.

-------
                                                           25% EDS Naphtha
                                                           Shale Diesel Marine
0
10
                       20
                        30          40
                           Emissions, ug/ kri
                                                            50
60
70
                         Figure  5.  BaP  emissions during FTP.

-------
                                     -23-

The Ames bioassay was performed on the extract  from  the  samples  taken as the
vehicle was operated  on the various fuels.  The  resultant data in  terms  of
revertants per microgram of extract are  presented  in Table 3.   The "distance
specific" Ames activity is shown in Table  4.   These data  take  into account
the total  particulate emissions and the percent extractables  from each fuel
blend.  In  reviewing  these data for strains TA 1537,  1538, 98  and  100, and
all of  the  fuels  except the Paraho JP-5, it is seen that  the  revertants per
microgram of extracts and  revertants per kilometer are  always  higher for the
synthetic fuels  than  for the base  fuel.  The  Paraho JP-5  fuel  occasionally
has lower  values.   The importance of this  has  not yet  been evaluated.  The
TA-1535 strain results were low or zero, which is normal for this strain.

Comparison  of  the results  of  this work with  previous   fuels  variables work
shows  few  consistent  trends.   However,  many of  the alternate  fuels tested
had higher aromatics  levels  and  lower  cetane  levels   than  the  base  fuel.
Previous work  has  shown that this could result in higher  emissions  of some
pollutants.  The same trend occurred with the alternate fuels emissions.

-------
                             -24-
TABLE . 3.  SUMMARY OF AMES BIOASSAY ANALYSIS OF ORGANIC
 SOLUBLES PROM PARTICDLATE MATTER COLLECTED DURING FTP
Fuel Code
EM-329-F
EM-453-F
EM-473-F
El«-474-F
EM-476-F
EM-476-F
EM-482-F
EM-485-F
Description
base DF-2
shale diesel
marine
PaTaho JP-5
Coal Case 5A
Broadcut
25% SRC-II
25% EDS
25% EDS,
naphtha
RLI-16
Activation
No.
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
NO
Yes
No
Yes
Model Predicted
Mean Slope, revertants/Ug extract
TA-1535
0.5
0.1
0.5
0.1
0
0.2
0
0.1
0
0.2
0.6
0.1
0.1
0.2
0
0.1
TA-1537
1.9
1.4
4.3
4.8
4.8
1.9
5.8
4.0
5.5
4.2
6.3
7.0
12.5
8.2
13.2
12.2
TA-1538
3.7
3.5
6.6
11.0
6.8
10.3
8.3
8.7
9.6
10.6
10.0
12.0
11.4
10.9
18.5
16.2
TA-9P.
6.-0
3.1
12.0
6.3
5.5
4.0
13.2
5.2
13.4
5.0
10.4
5.3
24.3
8.8
19.8
9.0
TA-100
17.1
7.2
30.5
14.5
14.3
5.7
23.8
20.7
23.8
61.3
13.7 '
19.7
16.3
17.4
8.6

-------
                                          -25-
                   TABLE 4-   SUMMARY OF AMES BIOASSAY RESULTS  IN
                          REVERTANTS PER DISTANCE DURING FTP
Fuel Code
EM-329-F

EM-453-F

EM-473-F

EM-474-F

EM-476-F

EM-478-F

EM-482-F

EM-485-F

Description
base DF-2

shale diesel
marine
Pataho JP-5

Coal Case 5A

Broadcut

25% SRC- II

25% EDS
--
25% EDS
naphtha
RLI-16
Activation
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes

TA-1535
18
4
24
5
0
7
0
5
0
12
34
4
5
10
0
4
Revertants per Kilometer •
TA-1537
70
51
204
227
177
70
296
204
316
242
365
406
620
407
486
449
TA-1538
135
128
313
521
250
378
423
444
552
610
580
696
566
541
681
597
TA-98
219
113
568
298
202
147
673
265
771
288
603
307
1206
437
729
331
TA-100
624
263
1444
687
525
447
1214
1055
2564
817
3553
794
978
809
641
316
Calculation incorporates particulate mass rates based on 47mm Pallflex filters,
 percent organic solubles extracted from Pallflex "20 x 20" filters, and data in
 Table  3.

-------
                                     -26-

b.     Heavy Duty Diesel

The heavy duty Diesel alternate  fuels  characterization  work has been planned
and funded  through  the  current Task Order  (Work Directive  No*  14,  Contract
Number  68-03-2884).   However, this  work has  not yet  begun  due to  higher
priority  M.A.N.  methanol  engine  work.   The  objective  of  the heavy  duty
Diesel alternate fuels effort will be  to  assess  the  pollutant emissions from
a heavy duty Diesel  engine that  is operated with  various  alternative fuels.
Final selection  of  the  fuels to be tested  has  not yet been made.   However,
they may  include a  national average  Diesel  fuel No.  2  (against which  the
other  fuels will be compared),  an  SRC-II/DF2  blend,  an  EDS/DF2  blend,  a
Diesel  2  Marine  (Paraho shale stock),  a blend  of  DF2  and  used lubricating
oil and the possibility of  new  or used  vegetable  oils blended with  DF2  or
neat.   Another less  likely possibility is  to  use a  SASOL  middle distillate
fuel.   One  factor  influencing the selection  of fuels  will be  their avail-
ability.

The engine  to be used  for  this work will be  a  Mack  EM6-300,  in-line  six
cylinder, 300 horsepower engine.   This engine has  been  received by Southwest
Research Institute and will  be installed  on the stand as soon  as the M.A.N.
methanol  work has  been completed.   The  testing will emphasize  transient
testing with some 13 mode  backup and will focus on  visible smoke,  regulated
gaseous   emissions,  individual  HC,   aldehydes,   phenols,    odor   index,
particulate  characterization as  well  as  a characterization of  the  organic
solubles extracted from the particulate.

-------
                                     -27-

2.  Methanol Fuel
    a.   Light Duty Vehicles

The light  duty vehicle methanol  characterization  work (3) has  consisted of
the testing of two light duty vehicles  (a  VW and  Ford Escort)  that  can use
100%  methanol  fuel  and  separate  vehicles  that  represent  their  gasoline
counterparts.   These  vehicles have been  tested  in their  "as  received"  con-
dition which  includes the  use of  a  noble metal  catalyst;  the  testing was
then  done  with promoted base  metal catalysts.  Also,  some  limited baseline
(no-catalyst)  work was  performed on  the Escort.   The emissions  for  which
analyses  have  been made   include  HC,  CO  and  NOx,   particulate,  unburned
alcohols  (methanol and  ethanol), aldehydes  and  ketones, individual  hydro-
carbons,  ammonia,  nitrosamines,  and  cyanide  and  cyanogen.   The individual
hydrocarbons were  methane,  ethane, ethylene,  acetylene,  propane, propylene,
benzene and toluene.   Also, on selected  vehicles  organic  nitrites have been
analyzed and  a gas chromatographic-mass  spectroscopic  (GC-MS)  analysis  will
be done for the emissions from one  of  the vehicles designed  for gasoline and
one that uses methanol fuel.

The vehicles  that  have been tested have been  on loan  from the manufacturers
or, in  the case  of the Escort  designed  for methanol,  on  loan  from  the
California Energy  Commission.  The vehicles have, for the  most  part,  been
tested and the  pollutant analyses are  currently being  completed and the data
compiled.  The vehicles that  use methanol  have  been  run on  100%  methanol
rather  than   a methanol/isopentane (94.5%/5.5%)   blend  on which they  have
apparently been manufactured  to  operate.  To set up   a  car  for  this  blend
versus pure methanol involves  fuel  metering recalibrations.   It has been our
experience that to operate a  vehicle  (the  Escort)  on the isopentane  blend
rather  than  100%  methanol  tends  to  increase the emissions of HC and CO.
Table 5  presents some preliminary  data  on the Ford  Escort  which  show  that
the hydrocarbon emissions are higher  for the  methanol/isopentane  blend.  CO
was also higher but there was  a slight NOx  reduction.   These  data have  to be
considered carefully, since  the  emission results  on the Escort  are  not  very
repeatable and it  was not  cost-effective to do a large  number of  tests  to
examine  test  repeatability  with  this  potential  blending   agent.   Other
reasons  for   the  use of  the  pure methanol  as opposed   to  the  isopentane

-------


-28-
Table 5

Effect of Methanol-Isopentane Blend
1981 Methanol-Fueled Ford Escort
HC
CO
NOx
HC
CO
NOx
HC
CO
NOx
HC
CO
NOx

Pure
Low
0.40
5.21
0.37

6.01
6.53
0.82

0.16
4.79
0.16

0.34
4.51
0.35
Composite
Methanol
High Average
0.53 0.43
7.26 6.03
0.42 0.40
Cold-Start1
1.51 1.21
7.48 6.97
1.05 0.90
Cold-Start2
0.23 ..0.18
6.85 5.52
0.23 0.19
Hot-Start
0.40 0.35
8.54 6.29
0.45 0.39
FTP g/mile
Methanol/ I sopentane
Blend
0.74*
6.92*
0.37
g/mile
2.00*
10.60*
0.87
g/mile
0.35
6.15
0.18
3 g/mile
0.50
5.58
0.37
*Car was not operated for four days prior to the cold-
 start 505.

1 bag 1 values
2 bag 2 values

-------
                                     -29-

mixture  is that  better  use  is  made of  scarce  characterization funds  by
developing a data baseline with pure methanol and then later perhaps looking
at  possible  fuel  variations  such  as the  isopentane  mixture.   Also,  the
isopentane is generally  put  in for cold start  operation at low temperatures
and  this  is  not needed at normal FTP temperatures at which  these tests are
being performed.  Also, it is the opinion  of  the author  that it has not been
shown  that isopentane  is the  best  compound  to mix  with methanol  for low
temperature cold start driveability and it may  not be used by refiners for a
mass  methanol market  but rather some other  compound  (e.g.  MBTE or light
boiling gasoline)  may work better and/or  may  be more commercially feasible.
A  VW representative (Dan Hardin) also feels this  way and  states that some
oil  companies  said this  at  the  recent Carnegie-Mellon  alcohol symposium in
Dearborn  (November 1, 1981).

Pure  methanol  was used  to  develop baseline data  in this  project.   Some of
the  data  that have been generated are presented  later  (e.g.  see Table 7).
Most  of the  data  taken on the Volkswagen appear to  be good.  The only major
difficulty  with  the  Volkswagen  data was  with  those  taken  with the foam
promoted  base  metal catalyst.  The catalyst had relatively low surface area
in  its   initial  condition,  and  the  substrate  was  broken  and  lost  in
                                                    ; 1
subsequent  testing.  The VW  was also  tested  with  a  promoted   base metal
catalyst  (Davex 908) on  a monolith substrate  with a volume 11% less than the
noble metal catalyst with  which  the VW  came.   In  any  event,  the catalyst
data for  the  two  vehicles are presented in Table 6.  From  Table  6 it can be
seen that the Escort's  promoted  base metal  catalyst had  much more   surface
area than the  VW's foam promoted base metal catalyst.   Also,  the Escort was
tested  with  4   biscuits,   at  the  recommendation  of   W.  R.  Grace.  (In
retrospect,  this  may have  been twice as  many  biscuits  as  should have been
used.)  This  resulted  in a  total catalyst surface area  for the Escort being
62,048/2484  or  25 times  more  than the VW.   The catalyst  material  is Davex
908,  on which  OMSAPC  is trying to get more data (e.g. loading, composition,
etc.).   It is important to have  this type of information  so one  can make a
preliminary  assessment  as to whether  the  Davex 908 may be a  less expensive
catalyst  than a noble metal catalyst  for this particular application.

-------
                                     -30-

                                       Table  6


       Table  of  Catalyst  Information for  Escort  and Volkswagen Methanol Vehicles
Vehicle

Shape of Cross
 Section

Dimensions per biscuit
 dia, cm
 axis, cm
 axis, cm
 length, cm

Volume, cnr*
Biscuits used
Total Volume
 of Catalyst used, cm^

Catalyst Surface to
Volume Ratio,cm2/cm3

Total Surface Area of
 Catalysts used,cm^
 Escort
 Elliptical
  7.6*
 12.7*
  7.2*

554
  2

 1108
Promoted
Base
Metal
Davex 908
Escort
Elliptical
6.8
14.4
7.2
554
4
216
Noble
Metal
Pt-Rh
VW
Round
10.2
15.2
1242
1
1242
Foam
Promoted
Base
Metal
Davex 908
VW
Round
10.2
15.2
1242
1
1242
Monolith
Promoted
Base
Metal
Davex 90£
VW
Round
6.8
14.4
7.2
2
1108
 NA
                28
62,048
                 NA
NA
2484
                         28
31,024
*Approximate
NA-not yet available

-------
                                     -31-

After  the  last VW promoted  base metal catalyst  run  was completed  with the
foam base  metal  catalyst,  the exhaust  system and dilution  tunnel  were dis-
assembled  and  catalyst fragments were  noticed.   At some point  the catalyst
had begun  to  fracture and about one half  of the catalyst was lost  from the
container.  Emissions  had  increased over each successive run which indicates
that   the  catalyst  efficiency  had  been  going  down  during  these  runs.
Southwest  Research   Institute  personnel   removed  the  remainder   of  the
catalyst,  replaced  the can  and  ran  an FTP  without  the catalyst.   (The car
had been started in the morning  and soaked until afternoon  and then run, but
since  it was  not soaked overnight it  was  therefore not an  official FTP but
close  to it  because the engine  was basically quite cold prior  to  its test-
ing.)  The data  from this test  are shown  in Table 7.   It must  be concluded
the  foam promoted base  metal catalyst data taken from the  Volkswagen are
going  to be  difficult to analyze in a meaningful way.  The HC, CO,  and NOx
emissions  were lower  with  the monolith promoted base  metal  catalyst compared
to  the foam  promoted base metal catalyst.  However,   the emissions  with the
noble  metal  catalyst  were lower than  those with either promoted  base metal
catalyst.  All of these results  are low mileage ones.

The data from  the  methanol-fueled Escort  may be  more  difficult  to evaluate.
The methanol-fueled  Escort that was shipped  to  Southwest Research Institute
(SwRI) for this  project had,  in the opinion of the SwRI personnel  who con-
ducted the program,  run poorly.  It had subjectively  evaluated  driveability
problems  and  could  not  follow  the  FTP  trace  well.  At  the end  of  the
emissions  testing  phase,  the vehicle  got to  the  point of not  running  at
all.   Subsequent checks with Ford  (Dr. Roberta Nichols, who is  in charge of
the Ford methanol vehicle  project) revealed  that  this  vehicle  was  one of the
first  three  shipped  to  California  and  as  such  was  sent  without  the
carburetor designed to prevent corrosion due to methanol.

-------
                                                                          Table  7
Pollutant
HC D. Level,6* g/ml
HC Emissions, g/ml
CO D. Level,8* g/ml
CO Emissions, g/ml
NOx D. Level,6* g/ml
NOx Emissions, g/ml
Fuels Economy, ml'/gal
Particulate, g/ml
Hethanol, mg/kra
Aldehydes and
  Ketones, mg/km
Individual HC, mg/km
Ammonia, mg/km
Cyanide and
  Cyanogen, mg/km
                                                             Table of Preliminary FTP Emissions
                                                             Data From Vehicles Run on Gasoline
                                                       and Methanol  -  Noble and  Base Metal Catalysts
Escort
Gasoline


Noble
Metal
Cat.
0.41
0.37
3.4
4.49
1.0
0.55
24.53
0.0092
0.0

0.1
96.0
N.A.*
Escort
HeOH


Noble
Metal
Cat.
0.41
0.43
7.0
6.03
0.4
0.40
12.56
0.0062
252.5

20.8
31.0
6.21
Percent
Change8


MeOH
Gas.
_
16. 2X
-
34. 3X
-
-27. 3X
-
-32. 6X
N.C.*
1
20,7001
-67. 7X
N.A.
Escort
MeOH

Promoted
Base
Metal
Cat.
_
0.31
-
1.51
-
0.35
12.74
0.0038
N.A.

2.1
24.6
3.34
Percent
Change
MeOH
Promoted
Base
Cat.
_
-27. 9X
-
-74. 9X
-
-12. 5X
-
-39. 7X
N.A.

-89. 9X
-20. 6X
-46. 2X
Escort
MeOH


Non
Catalyst
Noble
_
0.28
-
40.77
-
0.61
12.32
N.A.
N.A.

N.A.
N.A.
N.A.
VW
Gasoline


Noble
Metal
Cat.
0.41
0.11
7.0
1.08
0.4
0,16
23.76
0.0112
0.0

0.0
25.2
N.A.
VW
MeOH


Noble
Metal
Gas.
0.41
0.39
7.0
0.55
0.4
0.68
13.84
0.0047
272.5

6.4
3.2
N.A.
Percent
Change


MeOH
Gas.
_
254. 5X
-
-18. 5X
-
325. OX
-
-60. OX
N.C.

N.C.
-87. 3X
N.A.
VW@
MeOH
Foam
Promoted
Base
Metal
Cat.
-
0.87
-
3.60
-
1.75
13.66
N.A.
572.7

N.A.
10.0
N.A.
VW
MeOH
Monolith
Promoted
Base
Metal
Cat.
-
0.48
-
1.70
-
1.51
13.89
N.A.
N.A.

N.A.
N.A.
N.A.
VW**
MeOH


Non-
Catalyst
Baseline
-
2.08
-
7.51*
'-
1.87
14.09
N.A.
N.A.

N.A.
N.A.
N.A.
                                                                                                                            I*
                                                                                                                            NJ
N.A.
           0.00
                       N.A.
                                0.11
                                          N.C.
                                                  N.A.
N.A.
N.A.
                                                                                 N.A.
                             N.A.
                              N.A.
                                                                                                             N.A.
*   N.A. - Data Not yet Available
    N.C. - Not Computable
@   Data suspect due to catalyst problems
**  FTP not official
a.  Percent change identified by ratio given.  For example, in column 3, it Is MeOH/Gas., or (HeOH - Gas.) (100)
@*  D. Level*- Design emission level

-------
                                     -33-
As  soon as  the  new carburetors  became available,  Ford  and/or California
Energy  Commission personnel were  to  replace the carburetors  on these first
three vehicles such  that  they  would  then have the modified carburetor.  This
replacement unfortunately did  not  occur  for  this vehicle and the vehicle was
loaned  to  EPA without  EPA knowing  about the potential carburetor problem.
The end result was that the vehicle was  tested with a carburetor that was at
an  unknown  stage of  corrosion.  As such,  the  data  must   tentatively  be
considered representative  of  a malfunctioning vehicle.   After Ford replaced
the carburetor on the vehicle  with one designed  for  use with methanol fuel,
two FTPs and  HFETs were run and the  data compared  to  those from the vehicle
with the original  carburetor'as given in Table 8.

                                   Table  8

                   Average Emissions and Fuel Consumption
                    Data from Methanol-Fueled Ford Escort
                                  FTP
HFET
                         Original      New          Original  New
                         Carburetor    Carburetor Carburetor  Carburetor
Number of Tests
HC, g/mi*
CO, g/mi
NOx, g/mi
Fuel Economy, mi/gal
0.43
6.03
0.40
12.56
0.47
2.28
0.40
12.95
0.08
0.53
0.32
17.98
0.11
0.42
0.31
18.80
*Measured  HC  expressed  as  methanol.   Assuming  measured  HC  is  largely
methanol, HC  response  on  FID is multiplied by  ratio  of  molecular weights of
methanol and HC  (2.3).

-------
                                     -34-

These  data  indicate that  there was little  or no  effect  of  the  carburetor
corrosion on  the HC and  NOx emissions.   There was a  3%  (FTP)  increase in
fuel economy with the use  of the new carburetor and a  decrease  of  62% (FTP)
and 21% (HFET) in CO.  Therefore, one might  conclude  that  there  was at least
a  partial  negative  effect due  to the  original carburetor on the  emissions
data.

In reviewing the data in Table 7, it is  seen that  in  the case of the  Escort
the use of methanol as a  fuel reduces  NOx, particulate and individual hydro-
carbons.  However,  there is  a  very dramatic  increase  in  the aldehydes  and
ketones  with  most  of  this  increase   coming from  the  emission  of  more
formaldehyde  from  the  Escort  using methanol.   In  looking  at the  Escort
methanol-fueled  vehicle  with  a low  mileage  promoted  base  metal  catalyst,
reductions in HC, CO, NOx,  and particulate as  well as  aldehydes and ammonia
are  found.   However,  an increase  occurs for  cyanide  and  cyanogen emissions
from  zero  with  use  of a noble  metal catalyst to 0.11  mg/km  with  use of  the
promoted  base  metal  catalyst.   This  is below  the  level  of  concern  for
cyanide as  recently determined by  EPA  (4).   The durability  of  the promoted
base  metal catalyst  at  higher  mileages  is  not  known  and  is  an important
factor in  determining  whether  this   catalyst   would be  acceptable  for
commercial use on such vehicles.

In  looking  at the Volkswagen data,  it  is seen that the gasoline  version is
generally a  low emitter  of  pollutants.   When the vehicle  using methanol is
tested, HC  and  NOx levels were  higher.   The levels exceed the  level  of  the
standard  in  the case of  the NOx emissions  but the HC does  not  exceed  the
standard.   Lower levels were seen with  CO,  particulate,  and individual HC
when  the  vehicle using methanol was tested.   However,  a  large  increase in
methanol emissions  was noted.  These emissions were about  the same as those
from  the  Escort.   Also,  the aldehydes  were increased  but  not  to  the  same
level  as  seen with the Escort.  Ammonia  and cyanide data  are not available
at  this  time.   The  tests  also  showed that there  were  no  nitrosamine
emissions detected  in the  exhaust from any of  the  vehicles  tested  under  any
fuel  or catalyst situation.

-------
                                     -35-

Overall conclusions  that can be  reached  at this time  from the  program are
that vehicles can be  set up  such that they come close  to  meeting the levels
of  the emission  standards  at   low mileage  for HC,  CO,  and  NOx with  an
attendant  decrease  in  particulate  emissions  and  individual  hydrocarbons
relative to their gasoline fueled counterparts.   However,  methanol emissions
as well  as aldehydes and ketones are generally higher.   The  use  of  a  pro-
moted  base metal  catalyst and methanol as  a  fuel resulted  in low emissions
but again  this  is a  low mileage result.   However,  the  only nearly-complete
promoted base metal catalyst data  are  from  the Escort,  and the fact that the
promoted base metal catalyst was twice the size of  the  noble  metal catalyst
makes  a one-to-one  comparison  difficult,  especially  since the composition
and loading of  active material  is unknown.  There appears  to  be an increase
in the level of cyanide  and cyanogen  with the use  of the promoted base metal
catalyst.   This  is  something  that will  have  to  be  further  checked  even
though  the level  for  cyanide  appears  to be  below  the  level  of  concern
recently determined by EPA (4).

The  preliminary methyl  nitrite  data are  available;   methyl  nitrite  could
theoretically form from  reaction of methanol and  NOx in the exhaust.  Methyl
nitrite is of concern due to  its potential toxicity.  Methyl nitrite was not
found  in  the exhaust  of the gasoline fueled  vehicle  but was  found  at low
levels  (1  ppm)  in some of the tests of the methanol fueled vehicles.   It is
not known whether these  levels would present any environmental problem.

There  are  some data  that have  not yet been  reported  but  are expected  soon
which  should help  complete  a determination of the influence of  methanol use
on  vehicle  emissions.   These   missing  emission  data  are those for:   1)
selected pollutant results (see  Table 7  for the data Not^  Yet  Available), 2)
gas  chromatograph/  mass  spectroscopic data on  methanol  fuel  and gasoline
fuel exhaust streams, and 3) Ames  test data on the particulate extract.

-------
                                     -36-

b.     M.A.N. Methanol Engine

The M.A.N.  engine is  currently being tested  and this  testing  seems to  be
proceeding well even  though  there  were problems with initial  stages  of  this
project.  The  first  problem was due to shipping  and customs problems  that
ended  up delaying the  arrival  of  the  engine  until  the  first  part  of
December,  1981.   While  there  was  only  a  slight  delay  waiting  for  an
available  dynamometer,  the  dynamometer  that  became  available  developed
problems  in its   control  circuitry  which took  several  weeks  to  correct.
Finally,  the engine  was installed  towards the end  of  December and  testing
began.  However,  soon  after  testing began, the  ignition system failed.  This
has been  corrected but it now  appears that when  the ignition failed  it was
during  a  high  load,  high  speed condition that  may have resulted in  some
catalyst  destruction.   The catalyst has since  been replaced and  the  engine
is back running again  with testing being conducted.  The  end  result  of  this
is a delay in the original testing schedule.

A very small quantity of 13 mode emissions data is  now  available as given in
Table  9.   Table  9 also  includes  data  taken  previously  on  the  Volvo  dual
fueled  (Diesel fuel/methanol)  engine (5).   These  data  indicate that  the
M.A.N.  engine  equipped with a  catalyst  emits  low quantities  of HC,  CO and
particulate compared  to  the Volvo  dual fueled (Diesel  fuel/methanol)  engine
equipped  with  a  catalyst.  The  NOx  emissions,  however,  were  higher  than
those  from  the Volvo.   The remainder of  the  data  are  being processed and
will become available shortly.

-------
                                     -37-
                                   Table  9

             Table of  Emissions  and Fuel  Consumption  From M.A.N.
                 Methanol and Volvo Dual Fueled (Diesel and
                    Methanol)  Engine - Both With Catalyst
M.A.N.C

  Cold Start
  Hot Start
  Composite

Volvo
                     HCd
                0.19
                0.05
                0.07
                               Emissions, g/kW-hr
                          CO
0.80
0.40
0.46
           NOxD
8.91
9.30
9.24
          Part.
0.06
0.05
0.05
          Cycle BSFCa
          kg/kW-hr ~
0.796
0.711
0.723
  Cold Start
  Hot Start
  Composite
                0.36
                0.13
                0.16
5.54
3.29
3.61
7.44
7.38
7.39
0.26
0.34
0.33
0.538
0.515
0.518
c

d
BSFC is  in terms of dual  fuel rather than  Diesel  fuel for the  Volvo.
Approximately  80%,  by mass,  of  the  fuel consumed  during a  transient
cycle was  alcohol.   Heating  values  are:  Diesel at 18,400 BTU/lb  and
methanol at 8,550 BTU/lb.  The M.A.N. BSFC is in terms of methanol.

NOx  values  presented  here   are  based  on  continuous  measurement  by
chemiluminescence.  Intake humidity was  controlled  - NOx  correction of
1.00 used in all cases for transient NOx.

Preliminary data.

HC values reported here  are  based on indication of  HFID  (Beckman 402).
HFID response  has been reported  to  be very  low for unburned  alcohols
and some other species.

-------
                                     -38-

B.     Diesel Engine Characterization

       1.    Malfunction - Heavy Duty Diesel

The purpose  of  this work (6) was  to  test a typical bus engine  (DDAD 6V-71)
in a malfunction  configuration  that would be representative  of  a field con-
dition  in which  the bus  would  remain  in  operation  due  to adequate  per-
formance, but which might  be viewed as a "smoky"  bus.  It was  difficult to
decide on what  item would  cause a realistic malfunction without representing
a part failure.   It was decided that the  malfunction  configuration would be
made up  of individual maladjustments  to  the engine, which collectively would
simulate  a  malfunctioning  or worn  engine.  It was  decided  that  the  mal-
adjustments  would be made  in a stepwise  manner;  one  item  of maladjustment
would  be incorporated, then  a  hot-start  transient test would  be conducted
without   changing   dynamometer   control   parameters    from   the   baseline
configuration.  This would simulate a driver demanding  the  same performance
from a maladjusted/malfunctioning engine  as from  the  baseline/.stock engine.
The hot-start  transient emission test would quantify  the  relative influence
each  maladjustment  contributed   to  the   final  malfunction  configuration.
During  the  hot transient  test, emissions  of  HC,   CO, NOx,  particulate  and
visible  smoke (as determined  by an in-line  smoke meter) were measured.

The  first increment of maladjustment was the  substitution  of  50,000  mile
injectors obtained  from an in-use bus.   These  injectors had accumulated soot
deposits  on  the  tips,  but  from  outward appearance  seemed   to  be  in  good
condition with  no obvious  defects.  Injector timing was maintained the same
as  for the  baseline configuration.  Emissions  were measured over  a single
hot-start cycle.   Results   from  this  single transient  test are  presented in
Table 10 along  with the average hot-start emission results from the baseline
configuration.  The worn  injectors  caused the  CO emissions   to  increase by
67%  and  the particulates  to increase by 34%.   NOx decreased 10%  and  fuel
consumption  increased by 6%.

For the  second  increment  of maladjustment, the  timing was  retarded by 0.020
inch in  order  to  simulate  a worn cam drive train  which  occurs normally with
high  mileage  (7).   This  0.020 inch  increase   in setting  of  the  injector

-------
                                          -39-

       TABLE  AO   HOT START TRANSIENT EMISSIONS FROM DDAD 6V71 IN VARIOUS
            STAGES OF MALADJUSTMENT FROM THE BASELINE CONFIGURATION
                                                              Cycle BSFCa
Test
Configuration
Baseline
Hot Aug.
+50,000 Mile
Injectors
+0.020 Inch
Retard
+No Throttle
Delay
+Increase
Intake Rest.
Regulated
HCd
2.47
(1.84)
a
a
a
3.35
(2.50)
Emissions ,
CO
5.84
(4.36)
9.73
(7.26)
12.76
(9.52)
13.85
(10.33)
15.38
(11.47)
g/kw-hr ,
NOXD
9.79°'
(7.30)
8.78b
(6.55)
6.81b
(5.08)
6.77b
(5.05)
6.89C'C
(5.14)
(g/hp-hr)
Part.
d 0.70
(0.52)
0.94
(0.70)
1.34
(1.00)
1.45
(1.08)
1.45
(1.08)
                                                               kg/kw-hr,    Cycle Work
                                                              (Ib/hp-hr)   kw-hr, (hp-hr)

                                                                   0.313        8.24
                                                                  (0.515)     (11.05)

                                                                   -.331        8.21
                                                                  (0.544)     (11.00)

                                                                   0.343        8.09
                                                                  (0.565)     (10.84)

                                                                   0.339        8.24
                                                                  (0.558)     (11.05)

                                                                   0.342        8.22
                                                                  (0.562)     (11.02)
Continuous  HC  instrument failed—bag HC was used to process data.
These  NOx values  based on measurement of sample bag concentration—
Continuous  NOx instrument undergoing unscheduled maintenance.
Baseline  NOx emission by  continuous on-line measurement was 9.97
g/kw-hr.    Cumulative maladjustment NO^ emission by continuous
,on-line  measurement was  7.63 g/kw-hr.
Presented on the basis of bag measurement for comparison purposes.  .

-------
                                     -40-

plunger  pushrod  from  the  1.500  +  .005  inch timing  setting  effectively
retards the timing by approximately 2.8  degree  of  crank  angle (8).  As shown
in  Table 10,  the NOx  was  reduced  another  22%  and the fuel  consumption
increased by 3.6% with  the  retard  timing.   Both CO and particulate emissions
increased by about 30%.

Along with  the old injectors  and  the retard of  timing,  the  throttle delay
mechanism  was  adjusted  such  that essentially  no  throttle   delay  existed.
This  allowed  the  engine  rack  to  respond  immediately  to  the  throttle
command.  It appears  from the  results of the single  hot-start test  that the
absence  of  throttle  delay  had  comparatively  little  effect on  hot-start
transient  emissions,  although  both  CO  and  particulate  were increased  by
about 8% and NOx and BSFC were slightly reduced.

An  increase  in engine air intake  restriction was  added  to simulate  a dirty
air  cleaner  or  blower intake  screen.   The  data  presented in  Table  10
indicate that  the effect of  the  increased air intake restriction was minimal
with regards to NOx,  particulate and  fuel consumption,  but it did appear to
increase CO  emissions somewhat.   Results  from  the hot-start  transient  test
with the  additional  intake air  restriction were also representative  of the
                :  1
cumulative effect of all of the maladjustments.

Comparing  the  emission  results  from  the cumulative  maladjustments  to  the
average hot-start  emissions from  the baseline configuration  indicated  that
substantial  changes in  emissions had taken place.   The  HC appeared  to  have
increased by 32%,  CO increased  by a  factor  of 2.6,  NOx decreased  by  30%,
particulate  increased by a  factor of  2.1, and  fuel consumption increased by

-------
                                     -41-

Overall  engine operation  changed very  little  relative to  the changes  in
emissions.   Observed   power   under   the  baseline  configuration   and  the
malfunction configuration are  given  below with associated end-of-stack smoke
opacities.

           Baseline
           Max. Power;  440 ft Ib at 2100 rpm = 175.9 hp
           Smoke: 2.4%
           Max. TorqueJ 550 ft Ib at 1260 rpm = 132.0 hp
           Smoke: 8.0%

           Combined Maladjustment
           Max. Power:  420 ft Ib at 2100 rpm = 167.9 hp
           Smoke: 9.8%
           Max. Torque; 515 ft Ib at 1260 rpm = 123.6 hp
           Smoke: 23.5%

Even  though the  smoke and  particulate  emissions  significantly  increased,
maximum  power  and torque were  reduced by only  5%  and  6%, respectively.  One
could  infer  that  the malfunctioning engine  would  probably not  be  taken out
of  service  on  the basis of  this level  of  power loss.   On  this basis, this
cumulative  maladjusted  engine  was   selected   to  be  characterized  as  the
"malfunction"  configuration   and  detailed  emission   characterization  was
performed to obtain comparative data.

A  summary  of  13-mode composite emission results from both  the  baseline and
malfunction configurations is  given  in Table 11.  Thirteen mode composite HC
was  actually  23%  lower  for  the  malfunction  configuration  than  for  the
baseline   configuration.    This   was  contrary  to  indications   from  the
preliminary hot-start transient data.  Examining the modal  data, significant
decreases  in HC  occurred  in  the malfunction  configuration during  maximum
power  and maximum torque  conditions.  A 27% reduction in NOx,  primarily due
to  the retarded  timing, was accompanied by  an overall 6% increase  in BSFC.
Thirteen-mode CO emission increased by a factor of 1.8.

-------
                                     -42-
          Table  11    SUMMARY OF 13-MODE GASEOUS EMISSIONS FROM THE
                           DDAD 6V71 COACH ENGINE
                                        13-Mode FTP
    Test
Configuration

 Baseline
 Malfunction
Emissions,
HC
2.374
(1.771)
1.822
C1.359)
g/kW-hr
CO
9.922
(7.402)
17.832
(13,303)
(g/hp-hr)
NO*.
_9.595
(7.158)
6.977
(5.204)
BSFC
kg/kW-hr , ( Ib/hp-hr )
0.297
(0.488)
0.316
(0.520)

-------
                                     -43-

Smoke was measured  during  the 13-mode testing as well  as the FTP  for smoke
and  selected  steady-state points  along  the power  curve.  These  smoke  data
are  given  in Table  12  and  show significant increases  in almost  all power
points tested.   It  is  interesting that  all  of the relatively  large changes
in  smoke  occurred  during  the  high  power  conditions,  above  50%  load.
Relatively little change  in smoke was noted for  power points below the 50%
load condition.

Several  transient  heavy  duty  engine dynamometer  tests  were  run in  both
engine  configurations.   The  average  transient  emission  values from these
tests  are  given in Table  13.   In  comparing  the  two  configurations,  the
malfunction  transient  composite results  showed  a  slight  decrease  in  HC,
similar to that  indicated by  the 13-mode results.   Particulate and CO levels
under  the  malfunction  condition  were  substantially  increased  over  the
baseline  levels.  Composite  NOx emissions  under  the  malfunction  condition
were  26%  lower  than baseline levels.   Composite  fuel consumption was  also
increased, as expected, with the malfunction.

Table  14  summarizes the  modal  particulate  results  and  also  gives computed
7-mode composite results  from both test  engine configurations.  In addition,
these data are  presented  graphically in  Figure 6.   Preliminary maladjustment
data had indicated  substantial increases in smoke  and particulate.  From the
steady-state  data,  it  appears  that   the  increases  in  particulate  were
primarily due to increased  particulate emissions above  the 50% load level as
illustrated  in  Figure 6.   Malfunction 7-mode  composite  particulate  was 2.6
times  that  of   baseline  configuration  due  to the  significant  increase  in
particulate emissions at maximum power and torque.

-------
                       -44-
Table 12  SMOKE OPACITY FROM THE  DDAD  6V71  COACH  ENGINE
Smoke Opacity, %
Configuration


Baseline
Malfunction


Steady^-State

Mode
1
2
3
4
5
6
7
a
9
10
11
12
13
13-rMode FTP

RPM Power, %
Idle
1260
1260
1260
1260
1260
Idle
2100
2100
2100
2100
2100
Idle
—
2
25
50
75
100
—
100
75
50
25
2
__
"a" "b"
3.3 6.9
26.8 19.5
Smoke Opacity
Smoke
Baseline
0.2
0.2
0.3
0.4
0.9
8,6
0.3
2.3
0.5
0.3
0.3
0.3
0.2
"c"
~773
38.6

Opacity, %
Malfunction
0.1
0.1
0.1
0.3
2.8
23.5
0.4
9.5
3.9
1.7
1.3
1.1
0.1
Power Curve Smoke










RPM
2100
1900
1700
1500
1300
1260
1200









Smoke
Baseline
2.5
2.2
3.7
4.1
7.3
7.5
10.5
Opacity, %
Malfunction
10.0
11.3
14.8
16.3
23.5
—
—

-------
                         -45-
Table 13   SUMMARY OF AVERAGE TRANSIENT EMISSIONS
         FROM THE DDAD 6V71 COACH ENGINE
                                               Cycle BSFC°
Cycle
Type
Cold
Start
Hot
Start
Transient
Composite
Bus
Cycle
Regulated Emissions, gAw-hr, (g/hp-hr)
HC

2.49
(1.86)
2.47
(1.84)
2.47
(1.84)
2.72
(2.03)
CO
Baseline
6.03
(4.50)
5.84
(4.36)
5.87
(4.38)
4.65
(3.47)
NOxE
Configuration
11.69
(8.72)
9.97
(7.44)
10.21
(7.62)
10.27
(7.66)
Part.

0.86
(0.64)
0.70
(0.52)
0.72
(0.54)
0.83
(0.62)
kg/kw-hr,
(Ib/hp-hr)

0.372
(0.612)
0.313 .
(0.515)
0.322
(0.529)
0.339
(0.557)
Cycle Work
kw-hr, (hp-hr

6.77
(9.07)
8.24
(11.05)
8.03
(10.77)
3.31
(4.44)
Malfunction Conficruration
Cold
Start
Hot
Start
Transient
Compete ite
Bus
Cycle
2.18
(1.63)
2.18
(1.63)
2.18
(1.63)
2.48
(1.85)
16.58
(15.17)
16.58
(12.37)
17.12
(12.77)
20.72
(15.46)
7.53
(5.57)
7.53
(5.62)
7.52
(5.61)
7.98
(5.95)
1.66
(1.46)
1.66
(1.24)
1.70
(1.27)
1.97
(l'.47~)
0.338
(0.579)
0.338
(0.556)
0.340
(0.559)
0.345
(0.567)
8.37
(11.44)
8.37
(11.22)
8.39
(11.25)
3.80
(5.09)

-------
                                     -46-
      Table 14   SUMMARY OF MODAL PARTICULATE EMISSION FROM THE DDAD 6V71
Test Condition
Test
Particulate Rate
rpm/load, %
1260/2
1260/50
1260/100
Idle
2100/100
2100/50
2,100/2
Configuration
Baseline
Malfunction
Baseline
Malfunction
Baseline
Malfunction
Baseline
Malfunction
Baseline
Malfunction
Baseline
Malfunction
Baseline
Malfunction
mg/m3 exh.
12.45
11.48
22.27
25.67
161.46
661.88
8.64
6.17
74.89
224.56
42.37
31.32
19,72
18.70
g/hr
7.54
6.72
13.59
15.08
98.93
389.60
1.53
1.05
71.27
205.40
39.97
28.40
18.57
16.94
Composite

Baseline
Malfunction
Brake Specific
g/kW-hr
0.70
1.84
r
g/kW-hr
4.21
3.78
0.28
0.33
1.01
4.20
—
0.54
1.63
0.61
0.45
6.88
7.09
of 7-modes
g/kg fuel
2.00
1.70
1.12
1.26
3.96
15i40
1.82
1.09
1.99
5.63
1.91
1.34
2.02
1.81

Fuel Specific,
g/kg fuel

2.27
5.61

-------
                                    X
                                    -47-
  130
  120
  110
  100

&
 u
•rl
 fl

                  ^: L^-.r f:^O 'Malfunction

                                                Rated Speed
100       50         2

   Intermediate Speed
                                                                  100
                             Percent of Full Load


Figure 6   Modal Particulate Rates from the DDAD 6V71 Coach Engine

-------
                                     -48-

The  soluble  organic fraction  (SOF)  was determined  from both  transient  and
steady-state particulate  samples  from  both  configurations*  Table  15  gives
the  percent  of  the total  particulate  soluble  in  methylene chloride  along
with  the  composite soluble  fraction over the  seven steady-state  modes  and
the transient cycles. The  percent  of SOF was substantially lower  for  all of
the  malfunction  conditions  relative  to  the  baseline  configuration.   The
power specific  SOF  was  also  lower  for the transient cycles but  the same  for
the  steady  state  composite.   The  7-mode  composite  showed  no  difference
between the malfunction and  the baseline  configuration on  the  basis of brake
specific emission of SOF.

The  Ames  bioassay  was  performed  on  the  SOF samples taken from  the  engine
operating  in  the baseline and malfunction configurations.  The  results from
this  work  showed  no  discernible  difference   in   Ames  response  when  the
baseline sample  data were compared to the malfunction sample data (9).

Aldehydes  were  measured  using the  DNFH procedure.  A  summary of aldehyde
data  from  transient  operation   is  given  in Table   16.    Formaldehyde,
isobutyraldehyde and  benzaldehyde  were  the only aldehydes  detected over  the
transient  cycle.   Formaldehyde was  detected  from   both cold  and  hot  cycle
exhaust  samples, with slightly higher  levels detected  from the malfunction
configuration.   Essentially,  no  aldehydes  were detected  over the  13-mode
test  in  either configuration,  although some  traces  of  isobutyraldehyde were
found over the  baseline bus  cycle.

The  levels of  formaldehyde were higher  in the malfunction configuration than
the  baseline.   They were higher by  26% for  the cold  start and 76%  for  the
hot  start  [(Malfunction - Baseline)/Baseline) x  100].

-------
                            -49-
Table 15   SUMMARY OF CYCLE AND  COMPOSITE  SOLUBLE  ORGANIC
         FRACTION FROM THE DDAD  6V71  COACH ENGINE
Test
Cycle
Composite
7-mode
Composite
Cold Start
Cycle
Hot Start
Cycle
Transient
Composite
Bus
Cycle


Cycle Composite Soluble
Baseline
% SOF q -SOF/kW-hr
28.9
56.3
56.1
56.2
64.6
0.20
0.49
0.39
0.40 .
0.54
Organic
Fraction
Malfunction
% SOF
10.7
13.0
18.0
17.1
17.9
g SOF/kW-hr
0.20
0.26
0.30
0.29
0.35

-------
                                       -56-
              Table 16  SUMMARY OF ALDEHYDES FROM TRANSIENT OPERATION
                             OF DDAD 6V-71 COACH ENGINE
               Transient
Configuration    Cycle
                        Isobutyr-
Units     Formaldehyde    aldehyde
Benzaldehyde
Baseline Cold Start mg/test
mgAw-hr
mg/kg
Hot Start mg/test
mg/kw-hr
mgAg
Bus mg/test
mg/kw-hr
mgAg
Malfunction Cold Start mg/test
mg/kw-hr
mgAg
Hot Start mg/test
mgAw-hr
mgAg
Bus mg/test
mgAw-hr
mg/kg
190
27
76
170
21
67
— —


240
28
79
300
36
110
__


180 33
25 4.7
70 13
44
5.4
17
40
12
36
43
5.0
14
'79 —
9.5
28
_ _ __


Note:  No  acetaldehyde

-------
                                     -51-
2.    Normal Operating Conditions

Since the  last  ECTD characterization report, no work  has been done  in this
area.   Some  funds are  available for  the  work on  heavy duty  Diesels  under
normal  operating  conditions  through  EPA   Contract   No.   68-03-2706   with
Southwest  Research  Institute.   However,  work in  this  area  has  not  been
possible because  of a  lack  of  availability  of  dynamometer capacity due to
SwRI commercial work  and  due to dynamometer  capacity  being  preempted by the
Volvo dual-fueled  engine  and M.A.N.  methanol engine work of  EPA.   However,
work in this area  will  begin as  soon as the  M.A.N. engine  and the alternate
fuels heavy  duty  Diesel engine work  has  been completed  and the  dynamometer
becomes available.  One possibility for work under  this area will be testing
of particulate  traps  for  bus engines.  CTAB  has obtained the  loan  of a DDAD
6V-71 bus engine, which is currently  at SwRI.  This engine  could  be used for
any  trap  work done  under  this  contract.  Another  possibility would be the
testing of the  new Chevrolet 6.2 liter Diesel engine  or possibly some  other
power plant.

C.    Aldehydes at High Mileage

1.    Summary of Data

The  major  objective of  this project  (10)  was to evaluate regulated  and un-
regulated  exhaust  emissions, particulate  and aldehydes  from  1978 and  1979
catalyst  equipped  automobiles  that  had  been driven  approximately  50,000
miles.  The  automobiles were tested as received and  after  a  tune-up to the
manufacturers specifications.  The resultant  data were then  compared  to data
that  had  been  acquired  on  similar  vehicles  that  had been tested  under
previous EPA contracts.

This high-mileage  aldehyde  study involved ten automobiles,   seven 1978  model
year  automobiles   equipped  with  oxidation catalysts,  one   1978  model  year
automobile  equipped  with a three-way catalyst  and  two   1979  model  year
automobiles  equipped  with three-way  catalysts.  Engine sizes  ranged from  a

-------
                                       -52-
98 CID  four-cylinder engine  to a  400 CID  eight-cylinder engine.   The un-
regulated  emissions  measured   included:   particulates,   metals  and   other
elements,  aldehydes, organic  sulfide,  organic  amines,   ammonia,  cyanides,
hydrogen sulfide and nitrous  oxides.

A large data base for the  cars  evaluated  and tested was generated under this
project.   This  large data base was  condensed and  summarized  in  Table 17,
which presents an average  of  the emissions of the  pollutants  for all of the
vehicles.  For  example, an average  of the  hydrocarbon emissions  of  all  10
vehicles   tested  in  this   program   in   the   "as   received"  condition   is
presented.  This is  compared  to the  average of the  HC emissions for the veh-
icles  after  a  tune-up.   These data  are  then  compared  to  the  average   HC
emissions  of  eight  low mileage  catalyst  vehicles tested in another project.
Additional comparison data are  provided on the average HC emissions for four
1970 non-catalyst vehicles,  also tested  in another project.   These data are
then provided  for the  remainder of  the  pollutants for which analyses were
made.

From Table 17,  trends  in  emissions  changes  can be  observed.   For example,
with  the 10 vehicles  tested in this program  the  average "as  received"   HC
emissions  were  780  mg/km  and the  average  "after tune-up"  HC emissions were
600  mg/km,  which  would  appear  as  though  the  fleet   experienced  a 23%
[((600-780)/780)(100) = 23]  decrease in HC emissions.  However, average data
can occasionally be  misleading.  Therefore, all of the data were analyzed  as
'to whether the  individual data trends supported the  trends  of the averaged
data.   The results  of  this  analysis  are  presented  in  Tables 18  and 19.
Again  using  the HC  example  to   clarify this,  the changes  in  HC between "as
received"  and  tuned-up  were  analyzed  for  all  of the  vehicles  (in this case
only  eight vehicles needed  tune ups).  This  showed  that  of  the  eight data
cases,  only three  vehicles  had lower HC  emissions  after tune  up.    Three
vehicles had  increased  HC  and two had no  change.   This,  then, seems to make
the 23% decrease shown  in  Table 17  seem less definite and it  was judged on a
subjective  basis that  the probable  trend  (right  hand column)  was "little
change"  rather  than a  "decrease"  that Table 17  would have suggested.   This
process was repeated for the  remainder of  the data.

-------
                                       -53-
                                    Table  17

                              Average FTP Emission Rate, mg/km
                   Ten High Mileage
                   Cars-This Project
    Emission
As-Rec'd
  After
Tune-Up
Hydrocarbons          780        600
Carbon Monoxide     9,200      6,610
Oxides of Nitrogen  1,340      1,020

Total Fartlculates     49         32
Aldehydes & Ketones     6           4
Organic Sulfides      0.2        0.1
Oirganic Amines        0.1        0.1

Ammonia                 7           9
Cyanide & Cyanogen      1           1
Hydrogen Sulfide      0.1        0.1
Nitrous Oxide          46         36
 Four 1970 Model
Non-Catalyst Cars
Previous Tasksa

    1,900
   17,100
    2,600
                             0,
                             0.
                    99
                    37
                     1
                     1

                     4
                     3
                    0.1
   Eight Low Mileage
  Catalyst-Equipped C
Previous Projects

       200
     2,525
       670
                               8
                               2
                             0.4
                             0.1

                              12
                               1
                             0.1
                              22
al)ata for four 1979 model  cars  from Tasks  4 and  5  of  this  contract,
 KPA Report EPA-460/3-81-020                                     '   •
bl)ata for eight 1978 and 1979 model catalyst-equipped cars from previous
 contracts, 68-03-2499, 68-03-2588, and  68-03-2697.   EPA reports
 KPA-460/3-80-003, -004, and -005.

-------
                                      -54-
                                   Table 18

                          Comparison of  "As-Received"
                         Data to "After Tune-Up" Data
                           To  Note  Effect  of  Tune-Up
                     on Emissions - Ten High Mileage Cars
   Pollutant
HC
CO
NOx
•Trend  in
Table  17

decrease
decrease
decrease
Number of Individual
Data Points with     Probable
    Same Trend*        Trend
Total Particulates    decrease
Aldehydes and Ketones decrease
Organic Sulfides      decrease
Organic Amines        same

Ammonia               increase
Cyanide & Cyanogen    no change
Hydrogen Sulfide      no change
Nitrous Oxide         decrease
        3/8
        7/8
        4/8

        5/8
        6/8
        3/8
        8/8

        4/8
        1/8
        8/8
        5/8
little change
decrease
little change

decrease
decrease
little change
same

some change
little change
no change
decrease
*The.first number represents the number  of  individual  data points that exhibit
the  same  trend  as  in  Table  17.   The  second  number  represents  the  total
possible.  In this case, 8 of the 10 vehicles required a tune up.

-------
                                       -55-
                                   Table 19

                           Comparison of Low-Mileage
                        Catalyst Equipped Cars Data To
                     Ten High Mileage Cars (After Tune-Up
               Data)  To  Note  Effect  of High Mileage on Emissions

                                      Number of Individual
                      Trend in        Data Points with     Probable
   Pollutant          Table 17            Same Trend*        Trend
HC                    increase              10/10          increase
CO                    increase               9/10          increase
NOx                   increase               7/10          increase

Total Particulates    increase               9/10          increase
Aldehydes and Ketones increase               6/10          some increase
Organic Sulfides      decrease               9/10          decrease
Organic Amines    _    no change             10/10          no change

Ammonia               decrease               3/10          little change
Cyanide & Cyanogen    same increase          5/10          little change
Hydrogen Sulfide      no change              8/10          no change
Nitrous Oxide         increase               4/10          little change
*The first number represents the  number  of  individual data points that exhibit
the same trend as Table  17.   The second number represents  the  total possible.
In this case, 10 vehicles were tested at the two mileage points.

-------
                                    -56-
In reviewing the influence  on  emissions  of  the tune up  (Table  18),  it would
appear that there would  be  little  change in a fleet sense  in EC,  a decrease
in CO, some decrease  in  NOx,  a decrease in  total  particulates  and aldehydes
and  little or  no  change  in  the  remainder  of  the  pollutants  for  which
analyses were made*   Table  19  presents the  probable trend  in emissions as a
function  of  accumulated  vehicle  miles.  This  analysis  showed a  probable
increase  in  regulated emissions  (HC,  CO and  NOx), and  total  particulates,
some increase in aldehydes  and ketones  (Table 17  indicates an  increase from
2 to mg/km,  low mileage  to higher mileage-tuned-up vehicle),  a  decrease in
organic amines and little or no  change in the  remaining  emissions.   The most
significant result of this  work is that aldehyde  emissions do  not  g reatly
increase  at high mileage.  Thus, even at high mileage,  it  appears  that the
catalyst results in good control of aldehydes.

-------
                                      -57-

V.  References

1.  Baines,  Thomas  M.,  "Summary of  Current Status  of  EPA Office  of Mobile
    Source   Air  Pollution   Control   Characterization  Projects",   Report
    EPA/AA/CTAB/81-18, August, 1981.

2.  Bykowski, Bruce B«, "Characterization of  Diesel  Emissions from Operation
    of  a Light-Duty Vehicle on  Alternate  Source Diesel  Fuels",  Draft Final
    Report  for  EPA  Contract No. 68-03-2884, Task  Specification 3,  November,
    1981.

3.  Data taken  from ECTD/CTAB  memo from Karl H. Hellman  to  Charles L. Gray,
    "Update  on  CTAB Methanol Projects", January 15, 1982.

4.  DeMeyer, Colleen  L. and Garbe, Robert J.,  "The  Determination of a Range
    of  Concern  for Mobile  Source  Emissions  of  Hydrogen Cyanide",  Report
    EPA/AA/CTAB/PA/81-13, August,  1981.

5.  Ullman,  Terry L.  and  Hare, Charles T.,  "Emission Characterization of an
    Alcohol/Diesel-Pilot   Fueled    Compression-ignition   Engine   and   Its
    Heavy-Duty  Diesel Counterpart",  Report EPA-460/3-81-023, August, 1981.

6.  Monthly  Progress  Report  No.  33  for  Contract  No.  68-03-2706,  July 20,
    1981.

7.  Springer,  Karl,  "Field Demonstration  of  General  Motors  Environmental
    Improvement Proposal  (EIP)- A Retrofit Kit  for CMC City  Buses", Final
    Report,  Contract  No. PH22-68-23, December,  1972.

8.  Letter  from Dave Merrion  (GM Detroit  Diesel Allison Division)  to Karl
    Springer (SwRI) discussing timing changes, March  15,  1972.

9.  Memo,  Craig A. Harvey  to Charles  L.  Gray,  titled  "Recent  Ames  Test
    Results", January 6, 1982.

10. Smith,  Lawrence  R.,  "Characterization  of  Exhaust  Emissions  from  High
    Mileage  Catalyst-Equipped  Automobiles",  EPA Report  No. EPA-460/3-81-024,
    September,  1981.

-------
                                      -58-
VI. List of Recent CTAB Characterization Reports

The   following   reference  list   contains   all   of   the  recent   in-house
characterization reports  written by various CTAB  personnel.   The  list  also
contains most  of the  recent  CTAB  contract  reports in  the  characterization
area.  The  NTIS  numbers,  where available, are  given for  these  reports.   In
cases where an access  number  has  been  requested  from  NTIS  and is  not  yet
available,  the notation "NTIS-PB" followed by several blank spaces is given.

-------
                                      -59-

                       Recent CTAB Technical Reports
 1.  "Summary of  Current  Status  of  EPA  Office  of  MSAPC  Characterization
    Projects",  EPA/AA/CTAB/PA/81-18,  NTIS  PB  82105909,  August 1981.

 2.  "Gasoline Equivalent Fuel Economy Determination for Alternate Automotive
    Fuels",  EPA/AA/CTAB/PA/81-16,  NTIS  PB  82120072,  August  1981.

 3.  "Summary of EPA &   Other Programs  on  the  Potential Carcinogenicity  of
    Diesel Exhaust", EPA/AA/CTAB/PA/81-19, NTIS  PB 82128018,  August  1981.

 4.  "The Determination  of a Range  of Concern for Mobile Source  Emissions  of
    Hydrogen Cyanide",  EPA/AA/CTAB/PA/81-13,  NTIS PB 82120098, August 1981.

 5.  "Determination  of  a  Range  of  Concern  for  Mobile  Source Emissions  of
    Ammonia", EPA/AA/CTAB/PA/81-20, NTIS PB 82120056,  August  1981.

 6.  "The Determination  of Range of  Concern  for  Mobile  Source  Emissions  of
    Sulfuric Acid",  EPA/AA/CTAB/PA81-21, NTIS PB 82117870,  August 1981.

 7.  "An Approach  for Determining  Levels  of Concern  for  Unregulated  Toxic
    Compounds  from  Mobile Sources", EPA/AA/CTAB/PA/81-2,  NTIS PB  82118167,
    July 1981.

 8.  "Nitrosamines  and   Other  Hazardous  Emissions  from  Engine  Crankcase",
    EPA/AA/CTAB/PA/81-15, NTIS  PB 2127960, June  1981.

 9.  "Review  of  the  Literature  and On-going  EPA Projects Comparing  Portable
    Dosimeters &  Fixed  Site Monitors  as  Accurate Indicators  of Exposure  to
    Carbon Monoxide", EPA/AA/CTAB/PA/81-14, NTIS PB 82123712, May 1981.

10.  "A  Review  of  the Compatibility  of Methanol/Gasoline  Blends with  Motor
    Vehicle Fuel Systems", EPA/AA/CTAB/PA/81-12, NTIS PB 82117904, May 1981.

11.  "Brief  Synoposis of  EPA  Office  of  Research  and  Development  and  the
    Health Effects  Institute Mobile  Source Work",  EPA/AA/CTAB/PA/81-10,  NTIS
    PB 82124421, May 1981.

12.  "Mobile   Source Emissions   of   Formaldehyde   and   Other   Aldehydes",
    EPA/AA/-CTAB/PA/81-11, NTIS PB 82118159,  May 1981.

13.  "Comparison of  Gas  Phase Hydrocarbon  Emissions  from LD Gasoline  Vehicles
    and  LD  Vehicles Equipped  with  Diesel  Engines",  EPA/AA/CTAB/PA/80-5,
    September 1980.

14.  "Summary  of  Responses  from   Manufacturers  EPA  Letter  Requesting  Car
    Interior/Nitrosamine Information",  EPA/AA/CTAB/PA/80-4,  August 1980.

15.  "Changes   in  Automotive   Sulfate  Emissions   with  Extended   Mileage,
    CTAB-2/ASE-FY 79-1,  January 1979.

-------
                                      r60-

                Some Recent CTAB Extramural Contract Reports

 1.  "Estimating Mobile Source Pollutants in Microscale Exposure  Situations",
    EPA-460/3-81-021,  NTIS PB 82101114,  July 1981.

 2.  "Nitrosamines in Vehicle  Interiors",  EPA-460/3-81-029,  NTIS PB  82125014
    September 1981.

 3.  "Unregulated Exhaust  Emissions  from  Non  Catalyst  Baseline  Cars  Under
    Malfunction Conditions", EPA-460/3-81-020,  NTIS PB 82101130,  May  1981.

 4.  "Emission  Characterization  of   an  Alcohol/Diesel-Pilot  Fueled   Com-
    pression-Ignition  Engine   and   Its   Heavy-Duty  Diesel   Counterpart",
    EPA-460/3-81-023,  NTIS PB 82154113,  August  1981.

 5.  "Characterization  of   Exhaust   Emissions  from  High  Mileage  Catalyst-
    Equipped  Automobiles",   EPA-460/3-81-024,  NTIS  PB  82131566,"  September
    1981.

 6.  "Sulfuric  Acid   Health  Effects",  EPA-460/3-81-025,  NTIS  PB 82113135,
    September 1981.

 7.  "Hydrogen  Cyanide  Health Effects",  EPA-460/3-81-026, NTIS PB 82116039,
    September 1981.

 8.  "Ammonia Health Effects",  EPA-460/3-81-027,  NTIS PB  82116047, September
    1981.

 9.  "Hydrogen  Sulfide  Health Effects",  EPA-460/3-81-028, NTIS PB          ,
    September 1981.

10.  "Formaldehyde  Health  Effects",  EPA-460/3-81-033,    NTIS   PB  82162397,
    December 1981.

11.  "Acrolein  Health  Effects",  EPA-460/3-81-034,  NTIS-PB  82161282,  December
    1981.

12.  "Methanol  Health  Effects",  EPA-460/3-81-032,  NTIS PB 82160797,  December
    1981.

13.  "Nitrosamine Analysis  of Diesel Crankcase Emissions",  EPA-460/3-81-008,
    NTIS PB 81212458,  March 1980.

14.  "Characterization of  Diesel  Emissions  as a Function of Fuel Variables",
    EPA-460/3-81-015,  NTIS PB 81244048,  April 1981.

15.  "Characterization  and  Research   Investigation  of  Methanol  and Methyl
    Fuels", EPA-460/3-77-015, NTIS  PB 2718998,  August 1977.

-------
                                    -61-


16. "Impact  of  Coal   and  Oil  Shale  Products  on   Gasoline  Composition
    1976-2000", EPA-460/3-76-035, NTIS PB 265478, December 1976.

17. "Assessment   of  Automotive   Sulfate   Emission  Control   Technology",
    EPA-460/3-77-008, NTIS PB 270263, June 1977.

18. "Gasohol, TBA,  MTBE Effects On Light Duty  Emissions",  EPA-460/3-79-012,
    NTIS-PB 80224082, October 1979.

19. "Characterization of  Gaseous  and  Particulate Emissions  from Light-Duty
    Diesels Operated on Various Fuels", EPA-460/3-79-008, NTIS PB 80122443,
    June 1979.

20. "Hydrogen  Cyanide  Emissions   from a   Three-way   Catalyst  Prototype",
    EPA-460/3-77-023, NTIS PB 279037, December 1977.

21. "Preliminary    Investigation    of   Light   Duty    Diesel   Catalysts",
    EPA-460/3-80-002, NTIS PB 81240327, January 1980.

22. "Regulated   and  Unregulated   Exhaust   Emissions   from   Malfunctioning
    Non-catalyst and Oxidation  Catalyst Automobiles",  EPA-460/3-80-003, NTIS
    PB 80190473, January 1980.

23. "Regulated and  Unregulated  Exhaust Emissions  from Malfunctioning Three-
    Way  Catalyst Gasoline Automobiles",  EPA-460/3-80-004,  NTIS  PB 8019084,
    January 1980.

24. "Regulated  and  Unregulated  Exhaust  Emissions  from  a  Malfunctioning
    Three-way  Catalyst Gasoline   Automobile",   EPA-460/3-80-005,   NTIS  PB
    80187446, January 1980.

25. "Characterization  of  Sulfates,  Odor,  Smoke,  POM  and Particulates from
    Light  and  Heavy   Duty  Engines-Part  IX",  EPA  460/3-79-007,  NTIS  PB
    80121551, June  1979.

26. "Characterization of  Tire Wear Particulates", EPA-460/3-81-036,  NTIS PB
    821153586, November 1981.

-------