EPA/AA/CTAB/PA/81-15


                               Technical Report


                  Nitrosamines and Other Hazardous Emissions
                            From Engine Crankcases

                                      by


                               Thomas M. Baines



                                  June, 1981
                                    Notice
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 Source Air Pollution Control
                      Office of Air, Noise and Radiation
                     U.S. Environmental Protection Agency
                              2565 Plymouth Road
                          Ann Arbor, Michigan  48105

-------
                                      -2-
                       Nitrosamines and other Hazardous
                       Emissions from Engine Crankcases
I.   Background
Under most operating  conditions,  the  crankcases  of automotive engines emit a
stream of  effluent composed of  gases and  particulate  matter.  Most  of  the
gaseous portion of  this  effluent stream originates at  the  imperfect  seal of
the piston against  the  cylinder  wall.  This "blowby" originates  in the com-
bustion chamber and,  after  "blowing by" the piston rings,  enters  the crank-
case  and  is then  vented.   A  large part  of  the  particulate matter  in  the
crankcase effluent stream appears to originate in the crankcase.

The crankcases  of  all gasoline  fueled  engines were  subjected to regulatory
control in  1968.   This  regulation  prohibited any crankcase  emissions  from
gasoline fueled light duty engines  and  resulted  in the  use  of total recircu-
lation of  these emissions  through  the engine.   Since  that  time,  crankcase
emissions  have  been  prohibited   from light  duty gasoline  engines  and  are
currently  prohibited  by  CFR  86.081-8  (c)  (reference No.  1)*.    For  light
duty  gasoline  trucks, crankcase  emissions are  prohibited  by  CFR   86.081-9
(c) (reference 1), and for heavy duty gasoline engines  by CFR   86.080-10(c)
(reference  1).   At  the  time  the  first   gasoline  engine  emissions  control
regulations were promulgated,  it was determined   that Diesel  crankcase  emis-
sions did not need to be so regulated  because of their low  HC,  CO,  and  NOx
content.   For many  years most light  duty  Diesels have used  crankcase  emis-
sions  recirculation.   Recently,  however,  some  light  duty  Diesel  manu-
facturers  have  eliminated  crankcase controls.   Until recently,  almost  no
heavy duty Diesel engines employed  crankcase  controls,  but  rather discharged
the effluent into  the atmosphere.  This situation will change in  1984 when
CFR   86.084 -  11  (c)  (reference   1)  takes  effect.  This will  require crank-
case  effluent control on heavy  duty  naturally aspirated Diesel  engines  but
not on turbocharged  or  Roots  supercharged Diesel engines.   Therefore,  most
bus engines would  be  permitted to exhaust their  crankcase  effluent  into  the
atomosphere.  In fact, since most heavy duty Diesel  engines  are  expected to
be turbocharged, most of these engines  will also  have  no mandated  crankcase
control.   The gas  phase  portion  of the crankcase  stream  contains pollutants
such  as HC,  CO, NOx, aldehydes  and other  gases.   These  exist at  levels  of
0.005 to 4.1 percent  of  the  corresponding  exhaust emissions (e.g.,  crankcase
emission levels of  HC are about   0.2  to 4.1  percent of the HC exhaust  emis-
sion  levels) (2).   The  gas phase also  contains  nitrosamines,  a  very strong
carcinogen(S).   These are emitted at levels up to 268.8 ug/hour (3).
*  Number in parenthesis identifies the reference, a list of which is
   found at the end of the paper.

-------
                                      -3-
The  particulate portion  of  the  Diesel crankcase  effluent  stream  consists
primarily  of heavy  hydrocarbons.   About  88%  to 98%  of  this  material  is
solvent-soluble  organic   matter  with  the   remainder   being  carbonaceous
particulate  and a  small  amount  of sulfate.   Analysis  of  this  particulate
indicates  that  the  soluble  portion is  largely a  lubricating oil-type  of
material which  leads  one  to  conclude that it  could  be  entrained  lubricating
oil  mist material  (3).   Fresh  lubricating  oil  appears  to  be  biologically
benign  (4),  but used  lubricating oils  have  been known  to be a  carcinogen
since  1935  (5).   More recent  work has  shown used  lubricating  oils  to  be
mutagenic, also (4, 6).

II.  Nitrosamine Emissions

Nitrosamines are  a group of  compounds  that  take the  general form of  RoN =
NO (7).  Lijinsky (8) has described  them as follows:

    "Among carcinogens  the  N-nitroso compounds are  the most broadly
    acting and  among  the  most potent.   They  comprise the directly
    acting nitrosamides  and  the  systematically  acting  nitrosamines,
    which  require  enzymic   activation   for   their   carcinogenic
    action.	More than  a hundred  N-nitroso  compounds  have  been
    tested for  carcinogenic  activity and  most of them have induced
    tumors  in  rats;  a  much  smaller   number has  been   tested  in
    hamsters, mice  or guinea  pigs  and, again, most of those tested
    have been carcinogenic."

In recent testing of Diesel  crankcase  emissions,  nitrosamines were  found to be
present  in all  of  the samples  taken (3).   The nitrosamine  levels  appeared to
be a function of the  lubricating oil used (brand and age),  the engine  and its
associated crankcase NOx  flow rate,  engine operating cycle, and  possibly other
factors not addressed by the experimental design.

The  major  influence on  Diesel crankcase  nitrosamine  emissions  appears to be
the  lubricating oil.   All engine lubricating  oils contain  an additive  package
designed to  help  the  oil  function  better in  high  pressure areas,  to  suspend
foreign  matter,   to  widen   the   viscosity   range  and   to  prevent  rapid
deterioration by oxidants and  acids.   Many  of these additives contain amines
and other nitrogen-containing  compounds.   The  research  described  in references
3 and  9 indicated that  the  interaction between  these  nitrogen-containing oil
additive compounds and the crankcase NOx and  elevated  temperatures  resulted in
the formation of nitrosamines.

Reference  (3)  indicated  that there  are large  differences  in  the amount  of
nitrosamines that  result  from the use  of  various oils.   In  order  to  quantify
this  effect, a  bench procedure  was  developed  to  determine the  nitrosation
potential  associated  with a  given   oil.   This yielded much  interesting data.
For example,  base oil  (before  the additive package  is added) has  no ability to
form nitrosamines  under  this  procedure.  However,   84%  of  the  62  samples  of
fresh   oil   that   were  analyzed  for   their   nitrosation   potential   yielded
dimethylnitrosamine (NDMA).  Of the  60  fresh oils that  were analyzed for their
nitrosation  potential, 38%  yielded  n-nitrosomorpholene  (NMOR).  (Few of these
oil   samples  had   detectable  levels   of   nitrosamines   before   artificial
nitrosation.)

-------
                                     -4-
The nitrosation  potential  for  NDMA of fresh oils ranged from  a  low of 0.6 ppb
to  a high  of  202 ppb;  a  range  of  337  fold,  dividing  the highest  by the
lowest.  Thus,  there  is  a  large difference in  the  ability of different brands
of  oils to  form  nitrosamines.   There  is also  a  difference  in  nitrosation
potential of  a given brand  of oil.   For example,  Amoco  300 SAE  30  from the
Whiting  refinery has a  much higher nitrosation  potential than  the  Amoco 300
SAE  30  from  the  Houston  refinery  because of different  levels  of  additive
required at the  two refineries.

Given that there is a wide difference  in  the  ability of different oils to form
nitrosamines,  it  would  follow  that  the  nitrosamine  emissions  from  a  given
engine's crankcase would vary  as  a function of  the oil.  This,  as  it  turns
out, was the  case in the  experimentation described in reference  3.   A single
heavy  duty  Diesel engine  (Mack  ETAY(B)   673A)  was  tested  with  four different
oils representing  a range of  different  nitrosation  potentials  as  measured by
the bench procedure.   The  results are presented  in Table  1 and  they  showed a
very clear  correlation  (r=0.97) between  nitrosation  potential and nitrosamine
emissions.


                                    Table  1
                  Table of NDMA in Nitrosated Oil Vs. Average
                     NDMA in Crankcase Emissions For Mack
                         ETAY(B) 673A HD Diesel Engine


                                   NDMA in                 Average* NDMA
	Oil	      Nitrosated Oil  (ppb)      Emission Rate (ug/hr)


Shell Rotella T (SAE30)              1                          4

Amoco 300 (SAE30)                   25                         36

Mobil Delvac 1200 (SAE30)           88                         96

Mobil Delvac Super (15W40)         200                        144
* Average of two measurements per mode.  The seven modal averages are
  then composited using distributed weighting factors based on 13 mode
  weighting factors.

The measurements for the data presented  in  Table  1  were taken after one hour
of  preconditioning  on  the  fresh  oil  so that experimental  consistency could
be  maintained.   Therefore,  the results  are  valid  only for  the  fresh  oil
case.  Nevertheless,  there appears to  be  some  influence due  to the  age  of
the oil on  the  nitrosation potential  of the oil  and  the associated nitrosa-
mine  emissions.   Some  heavy duty  Diesel engine manufacturers  supplied oils
for nitrosamine  and  nitrosation testing from in-use  engines.   These samples
included a  fresh sample and samples taken  at  various  in-use intervals.  Un-

-------
                                      -5-
fortunately,  most  of   the   oils   chosen  had  low  fresh  oil  nitrosation
potentials.   The  results  showed  that of  the  eight used-oil  series tested,
all but  two  of them had declining (or no  detectable)  nitrosation potential
levels.   On  the other  hand,  some  extended mileage  samples taken  from the
various  vehicles  showed significant  levels of nitrosamines.   Therefore, it
must be  concluded  that  the ability of  an oil to  form  nitrosamines probably
decreases with  time of  use.   The  rate at which this decrease  occurs has not
been quantified.  This  change in the  ability of  the oil to form nitrosamines
may be related  to the consumption or deterioration of the additive package.

The type of engine  also has an  effect  on the  nitrosamine  levels emitted.
Reference  3  describes   the  results  of  nitrosamine  emissions  measurements
taken  from  three  different  engines  operated  on one  type  of oil.   These
results  are  presented  in Table  2.   References  3 and  9  conclude  that  the
engine  variables   primarily  responsible  for  the  variation in  nitrosamine
levels  shown in Table  2 are   1)  crankcase flow 'rate  of  NO and  N02,   and
2)  volume  flow rate  of crankcase  gases  which influences  residence  time of
NOx with the nitrosatable amines.
                                    Table 2

                  Table of Nitrosamine Emission Rates of Four      \
           Different Engines Operated on Mobile Delvac Super (15W40)A
                                                                   \
                           NDMA Emission Rate,  ug/hr

                                                 Weighted^
    Engine                   Peak                Composite

    Mack ETAY (B) 673A       268.8                  135.4
    DDAD 6V-71 N              52.2                   11.0
    Caterpillar 3406          71.2                   35.8
    Mercedes 240D*            18.4                   13.8
* Light Duty Vehicle.  Data in "Weighted Composite" Column are Geometric
 Average of 2 Steady State Modes.
@ 7 mode composite - see footnote, Table 1
The impact that  these  emission levels has on  ambient  air nitrosamine levels
is not a straight  forward  issue  to  analyze.   Such an analysis is complicated
by lack  of  a crankcase emissions  dispersion  model.  However,  some  data can
be discussed in this regard.

-------
                                      -6-
Very  little  monitoring  of roadside  nitrosamines has  been  performed.   The
limited amount of monitoring performed  to  date  has  shown levels in the range
of  1  jug/m-*.   For  example,  Gordon (10)  sampled air  along roadways  in the
Los Angeles  basin  and found  levels  up to  1.1  jug/m^.  He  found  no evidence
for any specific point emission  sources for the nitrosamines.  He found peak
levels  at  about  8 am  and 6 pm.   He  feels that  there  is  a  high likelihood
that the source is mobile  source related (11).
Shapley reports  levels of NDMA  of 0.8 jig/m  on the  Cross-Bronx Expressway
in New York City (12)  and  infers  that  this  is probably mobile source related
but  could  not   identify  a  specific  mobile   source   for  this  finding.
Pellizzari  (13)  reported 0.1 ppb  of  diethylnitrosamine  as  well  as  DMNA in
the  Eisenhower Tunnel  in Colorado.   This  is also  probably mobile  source
related since  the  tunnel  is  an  area away  from industry  and since it  is a
motor vehicle tunnel.

As far  as sources of  this nitrosamine are  concerned,  few  such  sources are
confirmed except  for crankcases.   Some data was  reported by  Urban,  et al..
(14)   which were  in  the  form  of  mass  spectroscopy  results  at the  same
retention  time  as NDMA.   These  were  taken  from various vehicles  equipped
without catalysts and  with oxidation catalysts.  The  data are considered to
be inconclusive  evidence  of  nitrosamine presence in  gasoline fueled vehicle
exhaust.   GM  has   also   presented  data   that   can  be  considered  to  be
inconclusive with respect  to the identification of  nitrosamines  in gasoline
fueled vehicle exhaust (15).

Cadle et al..  (16) report  results of work done in search for amines (nitros-
amine precursors), under  the  theory  that such amines  may react  with nitrous
acid in the atmosphere to form nitrosamines.   Their conclusion  is  that "it
is unlikely that any  of  the standard  gasoline  cars  on the  road  today are
emitting significant quantities of amines"  and therefore little  liklihood of
gasoline  fueled  cars  contributing significantly  to the  nitrosamine  levels
reported.   Also, Hurn et al.. (17) could not detect  amines in the exhaust of
noncatalyst cars.  Consequently,  it appears  one  could conclude that there is
little data that show that  exhaust  from gasoline  fueled engines  (light  or
heavy duty) contributes to roadside nitrosamine levels.

Currently,  there  are  only two  confirmed sources  of mobile  source  nitrosa-
mines  and one  strong  indication  of  mobile  source  nitrosamines.   The  con-
firmed  sources  are  crankcase  emissions  from  Diesel  engines  and  vehicle
interior  emissions  (18,  19).  The strong  indication of  nitrosamines  in ex-
haust  is  reported  in reference  3.    While performing  engine  sampling for
crankcase nitrosamines,  raw  exhaust  emissions were  sampled  from  one  of the
heavy  duty  Diesel engines.   The  results of this showed emission  rates  of
about 13.6jug/min.   The method used was  one  that  was qualified for crankcase
emissions (i.e., a high NOx  environment) but not  specifically for raw engine
exhaust.  Therefore, the  results  should  be  considered as strongly indicative
of the presence  of  NDMA, but not  as  confirmed evidence.  Very  recent work

-------
                                      -7-
being  performed  at Southwest  Research Institute  (20)  has shown  no exhaust
nitrosamines  from a  light  duty  Diesel engine  (Fiat,  naturally  aspirated)
using  a  qualified methodology.   How  this  result  impacts  the  heavy  duty
Diesel engine result is not known.

How do  these  confirmed sources of NDMA contribute to the  NDMA levels found
along  roadways?   This  is a question which is  not  very  easy  to answer.   The
data indicate  that crankcase  emissions contain NDMA  at  concentrations up to
28  ug/m3  (3).    Roadway   concentrations   up  to   1.1   ug/m3   have  been
detected.   What  portion of  the roadside level  is contributed by crankcase
emissions?  No really  adequate dispersion model currently  exists  to compute
this.   One  way to approximate this might be  to  ratio the  numbers that  were
used in  the support  documentation for  the Heavy Duty Particulate rulemaking
(21).    Such an  approach yields  a NDMA concentration  of 19  x  10"^-^  g/m-^
from crankcases;  a  small  fraction  of  the  1.1 x 10~6 g/m3  NDMA  observed
along roadways.

If the  same method  (21)  were to  be  used for the tentative  Diesel exhaust
NDMA  emission  factor,  the  result  would  be  112 x 10   ~12g/m3,  again  a
small fraction of the observed roadway  concentrations.

Another approach would be to  look  at  the relative  hazard assoicated with the
levels   of   nitrosamines  observed   along   roadways.    Assume   a   roadway
concentration  of  1.1  ug/m3  of NDMA  (of which the crankcase  emissions would
contribute  a  part)  and also  postulate a hypothetical  commuter  spending  2
hours  per day breathing  such air  (which  can be  a  relatively conservative
assumption).   At  a  10  liters/min respiration  rate  and  an  assumed  total
pulmonary adsorption of the NDMA, this  person would intake
      (1.1 ug/m3)  (10 1/min)  (0.001 m3/!)  (2 hr)(60min/hr)  = 1.3 ug NDMA.


This  is  about  equivalent  to  the nitrosamine  level  of  one can  of  beer  or
several  strips  of bacon  (22).    Obviously,  the  amount of  nitrosamine intake
would  increase  with  increasing exposure.   Also, this  exposure  would also add
to  any exposure  from the  interior of the automobile.   Using the  EPA  risk
assessment model  (23)which is used  for drinking water risk assessment,  this
would  translate into an cancer  incidence of  0.36  per 100,000  populaton per
year.  Assuming 150 million Americans  are so exposed,  the number  of annual
cancer  incidents  attributable to roadside DMNA  concentrations of  1.1  ug/m3
would be 546.   However, as Fine points out  (23):

    "The animal data base  for the  low dose response  study is  based
    on the 1963 study of Druckrey.  Very  recent work  in  England has
    found  that  NDMA  causes  increased  tumor  incidence  in  rats  at a
    level  of  0.035  - 0.130 ug/1, which is 10 to 30 times  less than
    the earlier Druckrey study.   If the latest British data had been
    used  to  calculate the risk  assessment, the number of  incidents
    would have  been  increased 10  to 30 fold."

-------
                                      -8-
If one assumes  a  20  fold increase in incidents due to more  up  to date potency
data, this would result  in  10,920 incidents  of cancer per year  due to roadside
nitrosamines.   If  one were  to  assume only  1.5 million  persons  (0.68%  of the
total U.S.  population)  were  exposed to  the 1.1 jag/nH  levels,  the  number of
of cancer incidents would then be  109 per year.

The other confirmed  source  of nitrosamines  is  automobile interiors.   The work
by Fine  et  al.. (18,  22) has  shown  levels in new automobiles  as high as 0.83
ug/m^.   The  work done recently  by Smith  (19)  for  EPA (ECTD)  found  a maximum
level of 0.63 .ug/m-*.   This level decreases with vehicle operation  to  about
one  fifth  of  the  at-rest  concentration,  or  0.13  ug/m^  when  applied  to his
maximum  concentration.  Using  the  same assumptions  as   above,   a hypothetical
commuter  traveling  for  2  hours  per  day   (with  10  min/day  at the  at-rest
concentration)  would be exposed  to  0.21  ug of  NDMA.    Using  the up  to date
potency data for NDMA  and assuming only 0.68%  of  the population is so exposed,
21 additional incidents per year of cancer would occur.

The  crankcase  emissions from  a  light  duty  Diesel; engine  were  sampled  and  a
nitrosamine  (NDMA)   emission  rate of  18.4  ug/hr (9.2 >ug/m^)   was  determined
for a 50 mph steady  state  condition.   Therefore, light  duty Diesel  crankcase
emissions will  also  contribute  to roadside  nitrosamine  emissions if they are
emitted  into  the atmosphere.   Currently,  most  such  vehicles have crankcase gas
recirculation systems.   However,  some are  being equipped  with road draft tubes
to vent  the crankcase  to atmosphere.

No  nitrosamine  measurements  have been taken  of .gasoline  crankcase  exhaust
because  of  regulations  prohibiting   crankcase  venting  to  atmosphere  (1).
However,  from  the   available  evidence  (3),  it  can  be   concluded   that  such
engines  would probably  contribute even  more  nitrosamines  to   ambient  levels
because  oils  designed  for use  in gasoline engines usually  contain more of the
amine containing compounds.   This is  verified by  bench nitrosation  of used
gasoline-fueled-engine oils which usually show positive levels of nitrosamines.

III. Particulate
The effluent  stream from Diesel engine crankcases  is  composed of particulate
matter  as  well as  gases.   Table  3  gives some  particulate data  from several
engines.   The  particulate  emissions  are primarily  composed of soluble organic
matter, and the indications  are  that it is mostly  of  a  lubricating  oil nature
(2).  Therefore, most of the particulate may be entrained lubricating oil.
                                    Table  3

                    Table of Particulate and BaP Rates for
                      Three Heavy Duty Diesel Engines (2)

                    Particulate*     Percent     BaP,      Weight % BaP
Engine             Mass Rate, g/hr   Solubles   ug/hr       in  Particulate

DDAD 6V-71              0.80           88.2      25.0        0.0031
DDAD 6V-71              2.44           98.1      76.8        0.0032
Cummins NTC-350         1.01           93.0      10.2        0.00094
* 7 mode composite

-------
                                      -9-
Also, the data  in  Table 3 show that  the  particulate contains benzo-a-pyrene,
which is emitted at a rate of from 10 to 77 jiig/hr.

Again,  it  would  be  useful  to  know  what  hazard,  if  any,  these  particulate
emissions represent.   The benzo-a-pyrene  is  well  known  to be  a  carcinogen,
one  that does  require  metabolic activation.  Used  lubricating  oil  itself has
been known  since 1935  to  be a  carcinogen.   Twort  et  al.. (5) has  reported
used  lubricating  oils  as  being  carcinogenic  as  determined  by  mouse  skin
painting.   They observed  that  used  oils  are  more  carcinogenic  than  fresh
oils.  More  recent work done by Wang et  al..(4)  has shown  that unused  motor
oil samples were not mutagenic but that motor oil from  a  CFR single cyclinder
engine became  mutagenic after  43  hours of  running.  All  mutagenic  measures
were  made  by  the Ames  test,  strain  TA98.    Payne et  al. .   (6)  has  also
reported  the  mutagenic  nature   of  used crankcase   oils,  both   neat  and
fractionated.   Payne also reports (24) that  mutagens  (some of  them possibly
very potent) are found  in nitrosated  samples  of petroleum.   Finally,  there is
some  indication that used  lubricating  oil can contain  some  polychlorinated
biphenyls (PCBs) which are known to be carcinogenic.

IV.  Summary and Conclusions

The emissions from heavy duty Diesel  crankcases contain a number of hazardous
compounds.  Research has discovered some  of  them and it  may be  possible that
there are  some  that have not  yet been  quantified.   Nitrosamines   (a  potent
carcinogen in animals  and probably also  in  humans) are  emitted from engines
using fresh  oil.   These emissions seem to be  a  function of the type of oil
used  and  some  engine  parameters   such  as   crankcase   flow  rate  of  NOx
compounds.  There is some evidence that the emission rate of nitrosamines may
decrease with  time,  but  this  has not  been  thoroughly   investigated.   It  is
currently difficult  to  convert  the nitrosamine emission  rates  into  roadside
concentrations  due to  lack  of a model  tailored especially  for  that  purpose.
The observed roadside concentrations  are  quite  significant  and could possibly
contribute to several  hundred  cases  of cancer  per year.    The  only  confirmed
sources of  this nitrosamines are Diesel crankcases  and automobile  interiors.
Diesel  exhaust  is  also  a possible  source.    Spark  ignition  engines  are
probably not a  source  of either nitrosamines or  nitrosamine precursors  (ie. ,
amines).  Other  exposure  scenarios for  nitrosamines should  be  analyzed,  such
as  tunnels,  garages, bus  terminals,  etc.   The  role  of  crankcase  emissions
should  be   analyzed  when  evaluating  epidimiological   data taken  from  such
confined  areas.   The   highest   priority   seems  to be   acquiring  some  more
roadside nitrosamine measurments to confirm the limited data available.   Work
is also needed  to determine  the  atmospheric  fate  and reactions of  nitrosamine
(e.g. would  nitrosamines emitted  by  roadsides  have a  long  atmospheric  life
and widely diffuse into the urban air?).

-------
                                     -10-
Th e particulate  emissions  from Diesel  crankcases  contain what appears  to  be
mostly  entrained lubricating  oil.   Used  lubricating  oil has  been shown  to
contain  carcinogenic  compounds  such as  benzo-a-pyrene.   It has  also  been
shown  to  be carcinogenic when  tested  in  skin  painting experiments.   It  has
also been  shown  to  be mutagenic, both  neat  and fractionated.  Therefore,  it
can  be  concluded  that  the  particulate  portion  of  the  crankcase  effluent
stream  may  start   out   after  an  oil  change  at  a   level  containing  few
carcinogenic compounds but  the level of these compounds  increases  with time.
In  summary,  crankcases  emit  a  variety  of hazardous chemicals and  evaluation
of  the  costs  and  benefits  of the  control  of  these emissions  should  be
seriously considered.

-------
                                     -11-
References

1)  Code  of  Federal Regulations,  40 Protection  of Environment,  Parts  81 to
    99, Revised as of July 1, 1980.

2)  Hare,  Charles  T.,  Montalvo,  Daniel  A.,  "Diesel  Crankcase  Emissions
    Characterization", Final  Report  prepared for Task  No.  4 EPA Contract No.
    68-03-2196, May, 1977. '

3)  Fine, David H.,  Goff,  E. Ulku, "Nitrosamine  Analysis  of Diesel Crankcase
    Emissions", Final  Report prepared  for EPA  Contract  No.  68-03-2719,  EPA
    460/3-81-001.

4)  Wang, Yi  Y.,  Rappoport,  Stephen M.,  Sawyer,  Robert F.,  Talcott, Ronald
    E., and Wei, Eddie T. , "Direct Acting Mutagens  In Automobile Exhaust", in
    Cancer Letters, Vol. 5, pp. 39-47, 1978.

5)  Twort, C.C., Twort,  J.M. , "Induction of Cancer  by  Cracked Diesel Mineral
    Oils," The Lancet, 2, pp. 1226-1228, Nov. 30, 1935.

6)  Payne, Jerry F.,  Martins, Isabel, and Rahimtula, Anver,  "Crankcase Oils:
    Are They  A Major Mutagenic  Burden  In the Aquatic  Enviroment?",  Science,
    Vol. 200, pp.  329-330, April 21,  1978.

7)  Anselme, Jean-Pierre,  "The  Organic  Chemistry of  N-Nitrosamines:   A Brief
    Review",  in  N-Nitrosamines, Jean-Pierre Anselme, ed.,  American  Chemical
    Society, 1979.

8)  Lijinsky,  William,  "N-Nitrosamines  as  Environmental  Carcinogens",  in
    N-Nitrosamines, Jean-Pierre Anselme, ed., American Chemical Society, 1979.

9)  Goff, Ulku, E.,  Coombs,  James R., Fine, David  H. and  Baines,  Thomas M. ,
    "Nitrosamine  Emissions   from  Diesel  Engine   Crankcases",   SAE  801374,
    Baltimore, MD, October, 1980.

10) Gordon,  Robert  J.,  "Survey  for  Airborne Nitrosamines", Final  Report for
    CARB Contract No. A6-096-30, June, 1979.

11) Personal communicatons with Robert J. Gordon.

12) Shapely, D., Science, 191, 268(1976).

13) Pellezzari, E.D., EPA Report 600/7-77-055 for EPA, ORD, ESRL, 1977.

14) Urban, Charles  M.,  Garbe, Robert J.,  "Regulated and  Unregulated Exhaust
    Emissions  from  Malfunctioning Automobiles",  SAE  790696, Dearborn,  MI.,
    June 11-15, 1979.

-------
                                     -12-
15) General  Motors Advanced  Emission  Control  System  Development  Progress,
    submitted to  the  Environmental  Protection Agency, Dec.  15,  1976,  pp VIII
    - 24.

16) Cadle, Stephen H.,  Mulawa, Patricia A.,  "Low Moelcular  Weight  Aliphatic
    Amines in  Exhaust from Catalyst-Equipped  Cars",  Environmental  Science  &
    Technology, Vol.  14, No. 6, June, 1980.

17) Hum, R.W., Allsup,  J.R. ,  Cox,  F., EPA  Report 650/2-75-014  for  EPA,  ORD
    (RTF, N.C), 1975.

18) Rounbehler, D.P., Reisch,  J.,   Fine,  D.H.,  "Nitrosamines  in New  Motor
    Cars", Food and Cosmetic Toxicology, Vol. 18, pp.  147 to 151, 1980.

19) Smith,  Lawrence  R.,  "Nitrosamines  in  Vehicle   Interiors",  Draft  Final
    Report for EPA Contract No. 68-03-2588, May 1981.

20) Personal   conversation   with   Mr.   Charles   Hare,   Southwest   Research
    Institute, June 4, 1981.

21) Heiser, Daniel P., "An  Investigation of  Future Ambient  Diesel Particulate
    Levels Occurring  in Large-Scale  Urban Areas", EPA  Technical Report  No.
    EPA-AA SDSB 79-30, November, 1979.

    From TableAl,   the Heavy Duty  Diesel Truck (HDT-D) emission  factor is  2.0
    g/mi and the HDT-D VMT represents 25%  of  the total  VMT.   Combining these,
    the  HDT-D represents  40%  of  the  total  weighted  emission  factor  used.
    This  weighted  emission factor  was used  to  compute ambient  particulate
    concentrations  from Diesel  HD  truck.  Taking  the  ratio  of  the  HDT-D
    portion  of  the  total  resultant  ambient  concentration  to  the  HDT-D
    emission  factor  and then  multiplying  by  the  HDT-D nitrosamine  emission
    factor, the ambient  nitrosamine  concentration  is computed.   The  exhaust
    nitrosamine emission  factor is  used  in the same manner  to compute  the
    exhaust contribution to ambient  nitrosamine concentrations.

22) Fine,  D.H.,   Reisch,   J.,   Rounbehler,  D.P.,   "Nitrosamines    in   New
    Automobiles,"    in    N-Nitroso-Compounds:    Analysis,     Formation    and
    Occurrence,  E.A.  Walker,  M.  Castegnaro,  L.  Griciute, M.  Borzsonyi,  Lyon
    (IARC Scientific Publications No. 31),  1980.

23) Letter from David  H. Fine  to Thomas M.  Baines, December 14, 1979.

24) Letter from Dr.  Jerry  F.   Payne  (Research  & Resource Services,  Fisheries
    and Oceans, Government  of Canada)  to  Laurie Gallagher  (EPA), August  13,
    1980.

-------