LDTP  78-04
                       Technical Report
       Diesel Hydrocarbon Measurement - Series Filter Test
                                by

                         Eugene Danielson



                            March 1978
                              NOTICE

Technical  reports  do not necessarily represent the final  EPA
decision on regulatory  issues.   The are  intended to present a
technical  analysis of an issue and recommendations resulting
from  the assumptions and  constraints  of  that analysis.   Agency
policy  considerations or  data received subsequent to  the date
of release  of  this  report  may alter the recommendations reached.
Readers are cautioned to seek the latest analysis from EPA before
using the information contained herein.
              Standards Development and Support Branch
                Emission Control Technology  Division
            Office of Mobile Source Air Pollution Control
                 Office of Air and Waste Management
                U.S. Environmental Protection Agency

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                                 -1-
Filters were loaded by driving various cycles (FTP, LA-A and 50 mph SS)
and collecting the particulate material.  Wet filters are those on which
particulate was collected and no drying steps were taken.  Dry filters
were prepared by baking wet filters at 380°F for one hour.

Two different particulate collection systems were used for loading the
second filter.  One was an isokinetic particulate collection device.
designed to collect a large volume of diesel exhaust, and is called a
high volume sampler.  The other was the existing Scott filter holder and
heated probe set-up which is used to sample exhaust from the dilution
tunnel.

Results

The graphs attached are reduced reproductions of representative heated
FID traces taken during this testing.  Presented on these graphs arc the
level of hydrocarbon in the exhaust passing straight to the heated FID
(dashed line) and the level of hydrocarbon in the exhaust after passing
through the "loaded" filter (solid line).   Both are graphed as a func-
tion of time.

The data displayed in Figures 2, 3, and 4 were collected using wet
(unbaked) filters in the second filter holder while Figures 5, 6, and 7
used dry filters in the second holder.  The dry filters removed somewhat
more hydrocarbon than wet filters, as might be expected due to a lower
lever-of saturation.  No meaningful differences are evident due to the
other variables involved such as driving cycle, probe temperature, and
the holder used to preload the second filter.

From these graphs the following additional observations can be made:

     1.  The level of hydrocarbon concentration remaining in the exhaust
     sample after it passed through the loaded filter (solid line) is
     definitely lower than the concentration level in the once filtered
     exhaust sample (dashed line).       .

     2.  Hydrocarbons in the exhaust were removed by all combinations of
     hot and cold probe, and wet and dry filters.

     3.  In most cases the particulate indicated a trend toward satura-
     tion.  However, the particulate remained unsaturated after seven to
     ten minutes of exposure to the hydrocarbons (i.e., the filtered HC
     concentration never reached the once filtered level of HC).  This
     is probably due to insufficient time for the gaseous hydrocarbon to
     saturate the carbon on the filter at the low concentrations and
     flows involved.

These observations form the basis for concluding that carbonaceous
diesel particulate is capable of removing hydrocarbons from a diluted
exhaust sample, and that some or all of the hydrocarbon material exists
in a gaseous form in the tunnel as well as the atmosphere.

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                             -2-
 Summary

 The intent  of the current  light-duty  diesel  hydrocarbon  certification
 test procedure is to measure  total  hydrocarbon  emissions.   Arguments
 have been put forth that  this intent  may  not be correct  for diesel
 hydrocarbon measurements because  some of;  the heavier  hydrocarbons may
 appear in the atmosphere as diesel  particulate  and  may be  non-reactive
 in the atmosphere.   Testing has been  conducted  to determine whether or
 not the carbonaceous particulate  material collected on diesel  exhaust
 filters absorbs hydrocarbon material  at ambient ("cold") temperatures.
 The preliminary results of this testing indicate that the  carbonaceous
 diesel particulate is capable of  removing hydrocarbon from a diluted
 exhaust stream sample.  The implication of this testing  is that  some or
 all of the  hydrocarbon material collected on an unheated filter  may
 exist in the gaseous rather than  the  aerosol state  in the  tunnel as vrell
 as in the atmosphere.

 Discussion

 The current test procedure specifies  that light-duty  diesel hydrocarbons
 are to be measured at a temperature range of 300° to  390°F by  the heated
 FID system.  However, some hydrocarbons measured by this system  may not
 contribute  to the formation of atmospheric photochemical oxidant (i.e.
 may be non-reactive). This statement is  based  on the presumption that
 the higher  molecular weight hydrocarbons  in  diesel  exhaust would be
 particulate material if they  were not heated to the temperatures speci-
.fied.  Therefore, one of  the  basic  questions that must be  answered is
 whether or  not the carbonaceous material  collected  on an exhaust filter
 has the capability of absorbing hydrocarbon  material  in  a  diluted
 (i.e., "cold") exhaust stream sample.

 Testing has been conducted with the EPA Mercedes 300  D diesel  automobile
 in order to help answer this  basic  question. The results  of this testing
 indicate that the particulate material collected on a diesel exhaust
 filter does absorb hydrocarbon material.   This  in turn implies that at
 least part  or possibly all of the hydrocarbon material in  the  dilution
 tunnel, and hence in the atmosphere as well, is in  a.gaseous state
 rather than an aerosol state.

 Test Procedure

 Two filters were installed in series  immediately downstream of the
 dilution tunnel sample probe.  The  sample lines were  configured  so that
 the second  filter,  which was  loaded with  diesel particulate from a
 previous run, could be quickly switched in and  out  of the  diluted sample
 stream.  (See Figure 1 attached.)   Response  of  the  hydrocarbon to the
 loaded filter was measured by direct  hot  FID reading  while the vehicle
 was operated in a 50 mph steady state cruise mode.  Two  series of tests
 were conducted; one with  the  first  filter and probe both operated hot
 (380°F) and the other with the first  filter  and probe cold (^  100°F).

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                              -3-

It should be noted that the exhaust sample was passed through a clean
filter in order to establish  that it was in fact the particulate, and
not the filter that was removing hydrocarbon from the exhaust sample.
The clean filtered exhaust gave the same heated FID response as the un-
filtered exhaust.  Hence the conclusion v/as that the. carbon particulate
was removing the hydrocarbon from the diluted exhaust.

It should also be noted that the base or once filtered levels are not
constant from test to test.  This is considered to be due primarily to
the background hydrocarbon level varying from test to test.  However,
this does not affect the conclusion of this testing because they are
based on differences between the once filtered hydrocarbon level and the
twice filtered hydrocarbon level.

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                  -4-

                   FIGURE 1

         SERIES  FILTER  TEST  SET-UP
            HF.ID
Second
Filter
 First
Filter
         Valve
                                      Exhaust
                                      Probe
                                                    Exhaust
                                   Dilution Tunnel

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                                              FIGURE  2
                                   Series Filter Test Results
                                   EPA Mercedes (300 D)
                                   50 MPH Cruise     u
Second Filter and Probe Data
Loading cycle: FTP
Filter source: Scott & filter holder
Filter condition: Wet (unbaked)
Probe: Cold (unheated)
Test date: 9/21/77
                                                                                                                    "u
                                                                                                                    XI-
                                                                                                                    UJQ
                                                                                                                    -i
                                                                                                                    x"1
o
                                                                                 Time - Seconds

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          FIGURE 3
Series Filter Test Results
EPA Mercedes (300 D)
.50 MPH Cruise
Second Filter and Probe Data
Loading cycle: FTP
Filter source: High volume sampler
Filter condition: Wet (unbaked)
Probe: Hot
Test date: 9/26/77
prop
HC Concentration
                                                 Time - Seconds

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                                                    FIGURE A
                                         Series Filter Test Results
                                         EPA Mercedes (300 D)
                                         50 MPH Cruise
Second Filter and Probe Data
Loading cycle: Hot LA-4
Filter source: High volume sampler
Filter condition: Wet (unbaked)
Probe: Hot
Test date: 9/26/77
                                                               Once Filtered Level

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                                                                                                                           5 5

                                                                                                                           E-5
                                                                                                                           So
                                                                                                                           °z
o
                                                                                                                  (yOO
                                                                                       Time - Seconds

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                                                FIGURE 5
                                     Series  Filter Test Results
                                   .'... EPA Mercedes (300 D)
                                   'K 50 MPH  Cruise
                                               Second Filter and Probe Data
                                               Loading cycle:  FTP
                                               Filter source:  Scott & filter  holder
                                              .Filter condition: Dry  (baked at 380°F Ihr)
                                              ;Probe: Cold  (unheated)
                                               Test date: 9/21/77
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                                                    FIGURE 6
                                          Series Filter Test Results
                                          EPA Mercedes  (300 D)
                                          50 MPH Cruise      i :
'•. Second Filter and Probe Data
••Loading cycle: 50 mph cruise
• \Filter source: High volume sampler
-Filter condition: Dry (baked at 380°F
.Probe: Cold (unheated)
;Test date:  9/71/77  . ...,	
Ihr)
(o
                                                                                                                           5
                                                                                                                           u
                                                                                                                           oS
                                                                                                                           x
                                                                                                                           o
                                                                                          Time - Seconds

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            FIGURE 7
Second Filter and Probe Data
Loading cycle:  50 mph cruise
Filter source:  High volume sampler
Filter condition:  Dry (baked at 380°F
Probe: hot  Test  date;   9/16/7?
Series Filter  Test Results
EPA Mercedes  (300 D) <
50 MPH Cruise
                                                                       lift
                                                                                 Ihr)
           Time - Seconds

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