ENVIRONMENTAL HEALTH SERIES
Air Pollution
   SELECTION AND TRAINING OF  JUDGES
      FOR SENSORY EVALUATION  OF THE
          INTENSITY AND  CHARACTER  OF
                 DIESEL EXHAUST  ODORS
U. S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
             Public Health Service

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   SELECTION AND TRAINING OF JUDGES
     FOR SENSORY EVALUATION OF THE
       INTENSITY AND CHARACTER OF
           DIESEL EXHAUST ODORS
                  Amos Turk, Ph. D.
            Professor, Department of Chemistry
      The City College of the City University of New York
           Prepared under Public Health Service
                Contract No. PH 27 66 96
U.S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
                 Public Health Service
    Bureau of Disease Prevention and Environmental Control
          National Center for Air Pollution Control
                   Cincinnati, Ohio
                       1967

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    The ENVIRONMENTAL HEALTH SERIES of reports was estab-
lished to report the results of scientific and engineering studies of
man's environment: The community, whether  urban,  suburban, or
rural, where he lives, works, and plays; the air, water,  and earth he
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that appear in the publication number; the indicators are        '

               AP — Air Pollution
               AH — Arctic Health
               EE — Environmental Engineering
               FP — Food Protection
               OH — Occupational Health
               RH — Radiological  Health
                     Water Supply and Pollution Control
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    Reports in the SERIES will be distributed to requesters, as  sup-
plies permit. Requests should be directed to the Center identified on
the title page or to 5555 Ridge Avenue, Cincinnati, Ohio 45213.
      Public Health Service Publication No.  999-AP-32

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                        FOREWORD

    Exhaust  gases  emitted  by diesel  engines  are  characterized by
odors that are offensive in varying degrees to many members of the
general public.  The increasing use of diesel-powered trucks and buses
in urban environments has resulted  in widespread  public awareness
of the diesel exhaust odor problem.

    It has not been established at this time whether any health haz-
ards are involved; nevertheless, because the odors are unpleasant and
irritating to people, studies of their origin and possible elimination
are a necessary part of the over-all program of  automotive air pollu-
tion research conducted by the National Center for Air Pollution Con-
trol, U. S. Public Health Service.

    Several research organizations, working under PHS sponsorship,
are conducting  programs of  engine testing  and  chemical  analysis
designed to  establish the identity and relative concentrations of all
products of incomplete  combustion present in  diesel engine exhaust.

    To correlate these  chemical analyses with the presence of odors,
one must devise means of rating the odors,  both as to  quality and
intensity, on some sort of numerical scale. Satisfactory correlations,
once accomplished, would make it possible to evolve readily enforce-
able Federal standards for control of diesel exhaust odors — standards
based on chemical  composition rather than odor ratings and hence
less subject to human error  or bias.

    This report, prepared under contract for the Public Health Serv-
ice, outlines the development of training methods and chemical odor
standards by which human panelists  can measure the  quality and
intensity of diesel exhaust odors.  These techniques are being  applied
in all of the PHS-sponsored research involving air pollution by diesel
engines.
                               111

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                        CONTENTS

                                                         Page
Abstract 	vii

Introduction	  1

Environmental Conditions for Sensory Testing	  3

Selection of Judges for Diesel Exhaust Odor Studies	  5

The Training of Judges for Diesel Exhaust Odor Studies	 15

Acknowledgments	 19

Appendix A. Concentrations of Odorous Vapors in Test
    Chambers  	 21

Appendix B. Sensory Standards for Diesel Exhaust Odor Study .... 27

Appendix C. Statistical Derivations 	 35

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                         ABSTRACT

    Exhaust gases emitted by diesel engines are characterized by of-
fensive  odors.  These odors must be rated numerically by human
judges with the ultimate objectives  of  (1)  correlating  such ratings
with the chemical composition of diesel  exhaust and (2) establishing
Federal standards for control of diesel exhaust  odors.

    Judges are selected on the basis of (1) their ability to distinguish
among odors of different intensities and qualities,  and (2)  their be-
havior in subjective testing environments. The chosen judges are then
trained  to improve their performance in odor discrimination, to be-
come familiar with diesel exhaust odor,  and to rate the odor in terms
of intensity and quality standards that are provided to them for ref-
erence.  These standards comprise a scale of overall  odor  intensity,
and four odor quality scales  that  correspond to the descriptions
"burnt/smoky," "oily," "pungent/acid," and "aldehydic/aromatic."

    Appendices describe (A) the theoretical basis for  air purification
requirements in test chambers for odor  studies, (B) the composition
and makeup of the diesel odor standards, and (C) the mathematical
derivations of the statistical procedures.
                                vu

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                     INTRODUCTION

    When a person is exposed to diesel exhaust on the street or high-
way, he may sense odor, chemical irritation in the nose or eyes, sound,
velocity pressure of moving air, temperature gradients, impaction of
small particles, and the sight of smoke,  moving vehicles, and other
associated actions. When  the aggregate of such experience becomes
sufficiently unpleasant, the threshold for individual action is exceeded
and the affected person may voice a complaint or react in some other
relevant manner.

    Odor is undoubtedly the prime sensory attribute of diesel exhaust
under  the  typical circumstances of human  exposure.  The  sensory
evaluation  of diesel exhaust odor under different conditions of  dilu-
tion, engine type, engine operation, fuel, fuel additives, and exhaust
control devices will therefore provide part of the basis for specifying
permissible conditions of exposure.

    The sensory evaluations will be made  by human judges. Taken
as a group  to increase  the  precision  of  the  evaluations, the judges
constitute a sensory odor panel.  In serving on the panel, the individ-
uals will be called upon to rank diesel exhaust samples to which they
are exposed according to odor intensity and according to the quality,
character, or type of odor. Depending on dilution of the exhaust, some
samples will be chemically irritating (in the sense  of "pungent") and
odorous at the same time, even though the senses of irritation and odor
are physiologically distinct.  In some cases, therefore, the evaluation
continuum will, in effect,  comprise both types of sensations.

    The judges in these tasks express their evaluations of intensity
and quality in a quantitative way; they do not assume the role  of
individuals who express their personal preferences of "like" or "dis-
like."  The following general requirements are imposed for the selec-
tion and performance of such judges.

    1. They must have  satisfactory sensory ability  to  distinguish
among odors of different intensities and to discriminate among differ-
ent odor qualities.

    2. They must be  emotionally receptive to  tasks that involve
quantitative and  discriminatory judgments  without expressions  of
preference.

    3.  They must be trained for the specific tasks to be accomplished.

    4.  A non-distracting environment must be provided for the sens-
ory tests.

    5.  Standards should be established to provide a quantitative basis
for sensory measurements and to provide replicable anchoring points
that will facilitate interlaboratory comparisons.
INTRODUCTION

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      ENVIRONMENTAL CONDITIONS  FOR

                  SENSORY TESTING

    A space for sensory testing should be free of competing distrac-
tions. In-and-out visits  and socialization by non-participants should
be restricted, except in demonstration exercises. The area for prep-
aration and coding of test samples or make-up and dilution of exhaust
gas streams should be separated from  the panel members  and not
visible to them. Extraneous sounds, especially the sounds of operation
of test vehicles, should be inaudible during the tests. Color schemes
should be neutral and not striking.

    The test area should be provided with some means for space odor
control,  especially for  control of  the odors  introduced from the sam-
ples being tested. This may be accomplished either by local exhaust
of vapors from the test samples, or by general purification of the room
air through a recirculating device, preferably an  activated carbon
unit, or  by some combination of both methods. If a considerable vol-
ume of  air containing odorous diluted vehicle exhaust is spilled into
the space during the tests, then  the effectiveness of odor control by
general  recirculation through an  air purifying device will be limited.
The nature of this limitation is described in detail in Appendix A.

    When the tests are to be conducted and reported on an individual
basis without communication between judges, it is  desirable to have
separate booths or enclosures for  the individual panel members. When
the test is to be cooperative, with discussion and comparisons among
the judges, then a conference table setup is convenient.

    The panel moderator or chairman should be able to communicate
readily  and conveniently with all of the judges. The general atmos-
phere should be comfortable and relaxing, but also should encourage
the judges to be attentive  and serious.

    Several simple rules for conduct should be imposed. No smok-
ing, eating,  or drinking that is  not associated with tests should be
allowed in the test area. Women should be discouraged from the use
of perfumes  or perfumed cosmetics  just prior to  a test session.  A
period of about one-half hour or  more should be allowed after smok-
ing, eating a meal, or drinking  coffee,  before participation  in a test
exercise.
 ENVIRONMENTAL CONDITIONS

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      SELECTION  OF  JUDGES  FOR  DIESEL

              EXHAUST ODOR STUDIES

    There is no "magic number" of panel members.  Many  panels
number five to fifteen judges, and a number close to ten is probably
suitable for diesel exhaust sensory work. A large number of panelists
should be available for testing so that no interruptions need be caused
by temporary absenteeism or personnel turnover. The panel members
should not be divided, however, into "regulars" and "standbys." Some
rotation scheme should be set up so that no trained panel member is
allowed to go "stale."

    The major tasks that the odor judges will be expected to perform
are:

    1. To judge the relative intensity of diesel exhaust odors at dif-
       ferent dilutions.

    2. To discriminate among the different qualities of diesel exhaust
       odors.

    3. To combine (1) and (2) to give a composite profile.

    The judges will  be  expected to follow instructions, and  at the
same  time  to render independent judgments  reflecting  their own
sensations and report their findings.

    Four main tests for selection of judges  are recommended:

    1. The triangle test.

    2. The intensity rating test.

    3. The multi-component odor identification test.

    4. Demonstration of satisfactory test behavior.

These tests are described in detail in the following sections. Statistical
derivations of these tests are presented in Appendix C.


                   THE TRIANGLE TEST

    Three test samples  are presented at  the same time. Two are
identical, the third is different. The candidate is requested to identify
the  different or "odd" sample.

    In dealing with untrained candidates, the moderator should avoid
strange or objectionable materials. It is convenient to use dilute aque-
ous  solutions of food flavors. These are easy to-administer, and they
product  a minimum of initiation "shock" to the candidate. The solu-
tions may be smelled or tasted; in both cases, olfactory discrimination
is actually being used to make the identification. Materials that are
recommended are:
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      Flavorant            Approximate Concentrations

      Vanilla extract       To one quart of water add 1 or
      Lemon extract        2 drops of required extract to
      Pineapple extract     achieve a detection threshold at a
      Almond extract       level such that about 75% of the
      Rum extract         triangle scores will be correct an-
      Rose extract         swers'
      Mint extract

    The samples should be presented at ambient temperature in small
throw-away paper cups.

    Instructions are given as follows: "The object of this test is to
distinguish differences  between food  flavors that are very weak in
intensity.  The samples given to you consist of one or two drops of a
common food extract, like vanilla, almond, or  mint, in a quantity of
pure drinking water. You may smell or taste the samples, or  both.
Each test  consists  of three samples, two of which are the same and
one of which is different.  Your task  is to pick out the different or odd
one. You  do not have to identify the flavor, just choose which one is
different from the other two. Enter on your score sheet the code
number of the sample which you choose as the odd one."

    Present a trial test to familiarize the candidate with the proce-
dure.  This trial should be conducted at a higher level of intensity so
that the distinction is easy. Do not ask for a score. State the correct
answer verbally to the candidate. Answer any questions regarding
procedure. The purpose  of this  trial is to concentrate most of the
learning into the first experiment and to make the subsequent tests
independent of each other to a greater degree. Now administer and
score five triangle tests.

    Select the candidates on the following basis:

    List the candidates and their scores  (number of correct answers)
in order, highest score first.

    Refer to Table I to determine which  differences between scores
are significant.

    Decide how many panel members  you should select  from the
candidates available. Determine from the table at what levels there
are statistically significant differences between candidates and make
your selection accordingly. For these rough screening operations, it
is recommended that confidence limits be set at about 25 or  30%,
rather than the usual 5%.  This will have the effect of initial rejection
of most of the candidates that are likely to be unsuitable.

    Example I. There are ten candidates, who take five triangle tests
each.  We  need about five or six panel  members  from among these
candidates. Their scores are:
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          Candidate                 Number of correct answers
              A                                5
              B                                2
              C                                3
              D                                0
              E                                0
              F                                2
              G                                3
              H                                5
              I                                 5
              J                                4
        TABLE I — SIGNIFICANCE OF DIFFERENCES
           AMONG SCORES IN TRIANGLE TESTS

                  Difference between      Probability that at
  Number           two candidates in      least this difference
    of             number of correct       could have been
   tests                answers          obtained by chance
                          0                    100%
                          1                     44

                          0                    100%
                          1                     59
                          2                     10

                          0                    100%
                          1                     66
                          2                     19
                          3                      2

                          0                    100%
                          1                     71
                          2                     25
                          3                      5
                          4                     0.5

                          0                    100%
                          1                     74
                          2                     31
                          3                      9
                          4                      2
                          5                     0.1
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    Step I.  Choose an acceptable significance level.  In this case we
will choose 0.20-0.30 (70-80% confidence levels).

    Step 2. List the candidates in order of the  number of correct
answers they gave.

            Candidates                Number of correct answers
               A, H, I                              5
               J                                   4
               C,G                                3
               B,F                                2
               D,E                                0

    Step 3. Check Table 1 to determine how much of a difference in
the scores of two candidates is needed to give confidence that they are
significantly different from each other. In this example, the number of
tests equals 5, therefore, a difference of 2 or more in score indicates
a significant difference in performance.

    Step 4. Choose the candidates required. Starting from the top,
A, H, and I have a score of 5.  But the scores of candidates A, H,  I,
and J differ by less than 2; therefore this difference is not significant,
and we can consider these candidates to be  "equal."  If we need five
or six panelists and have no other candidates, we must add C  and  G
to the panel.  (J, C, and G can be considered  "equal.") The panel will
then consist of the first six: A, H, I, J, C, and G.

    Note that we could establish higher confidences in our selections
by giving more tests, say 20 or 25 instead of 5. This is not recom-
mended because the extra effort can be more profitably expended in
the screening of additional candidates.


              THE INTENSITY RATING TEST

    A series of dilutions  of an odorant in an odorless diluent is set
up. One sample is removed from the series. The candidate is asked
to replace it according to its odor intensity in the position from which
it was taken.

    For use in selecting  candidates, the odorant should be  fairly
strong when it is in pure form, and not toxic, unpleasant, or strange.
Any of a number of  fruity or fragrant odors are acceptable.  Some
possibilities are amyl acetate, eucalyptol, oil of wintergreen, or heptal-
dehyde.

     In the example that follows the odorant  is amyl acetate in  propy-
lene glycol (low-odor perfumer's grade). Amber 2-ounce glass bottles
with plastic screw caps are used.
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                                                 Concentration
                                                 (fraction by vol-
                                                  ume of amyl
                                                  acetate in the
  Bottle No.        Procedure                        solution)
      1       Add 10 ml amyl acetate.                    1

      2       Add  10 ml amyl acetate plus              %
              10 ml propylene glycol.  Mix.
              Using a 10 ml pipet, remove
              10 ml of the mixture and transfer
              to bottle 3.

      3       Contains  10 ml of material from           ^4
              bottle 2. Add 10 ml propylene
              glycol. Mix. Remove 10 ml of
              mixture and transfer to bottle 4,

      4       Contains  10 ml of material from           Vs
              bottle 3. Add 10 ml propylene
              glycol. Mix. Remove 10 ml
              of mixture and transfer to
              bottle 5.

    Continue this procedure until the mixture has no detectable odor
of amyl acetate. The total number of bottles thus prepared will be
approximately 20.

    If the bottle number is designated n,  then the concentration in
any bottle equals 21-n.

    The  bottles must appear identical and  must be  consecutively
numbered so that the numbers are not visible to the candidates. Labels
can be put on the bottoms of the bottles or on the face of the bottle
if the label is obscured by wrapping with  aluminum foil during the
test. The bottles are lined up in sequence in front of the candidate.

    The following instructions are given: "The 20 bottles lined up in
front of you all contain solutions of amyl acetate, which is a synthetic
banana oil.  They differ from each other in odor strength, the most
intense odor is on the left, and the intensity gradually gets less from
bottle to bottle toward the right.  The last bottle on your right has so
little banana oil odor that it may not be detectable at all. In the test
you are about to perform one of these bottles will be removed from
the series, from a position unknown to you.  The task will be to replace
it in the proper  location in the series, the location from which it was
taken. If it is replaced in its proper position, it will smell stronger
than the bottle  on  its right and weaker than the bottle on its  left.
Proceed as follows.  First familiarize yourself with the odors  of the
bottles in the series. Start from the right (number  20)  remove the
cap, sniff gently and recap. Then do the same for about every other
bottle going to your left. Remember, the odors will be getting stronger
toward the left  and you will fatigue your  sense of smell temporarily
SELECTION OF JUDGES

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if you sniff too long at the more intense odors.  You need not smell
every bottle in the series at this stage of the test." (After a brief time
for familiarization . . . ) "Now leave the room."  (The tester removes
one bottle, and rearranges the others to obscure the gap. The removed
bottle is placed in front of the remaining 19). "Now come back into
the room and  replace the  bottle in the location where it  belongs in
the series."

    Statistical scoring procedure: The same specified test program,
in randomized order, must be used for each candidate.  This program
consists of four tests, in which the following bottle numbers are  suc-
cessively removed in random order: 3, 8, 12, and  16.  This presupposes
a dilution series of at least 20 bottles.  The highest test bottle number
must be 4 less than the number of bottles  hi the series.  If the total
number of bottles is, say 17, the test sequence could be 3, 7, 10, 13.

    Step 1. Score as follows:

        Positions removed               Score (higher  number
       from correct location                  is worse score)
                 0                                0
               ±1                                1
               ±2                                4
               ±3                                 9
               ±4 or more                        16

    Step 2. Refer to Table 2 to determine which differences between
scores are significant.

         TABLE 2 — SIGNIFICANCE OF DIFFERENCES
        AMONG SCORES IN INTENSITY RATING TEST

       Differences between               Probability that at least
        scores of any two                this difference could have
           candidates                  been  obtained by chance
               18                              30%
               20                              25%
               23                              20%
               25                              15%
               29                              10%
               34                               5%
               44                               1%
               56                            1/10%

   Example 1. A  candidate performs as follows:

         Missing bottle                   Replaced hi position
                8                                 7
               12                                 12
                3                                 5
               16                                 6
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    What is the candidate's score?

     Bottle           Positions removed from
    Number             correct location              Score
        8                   8—7=   1                1
        12                 12—12=   0                0
        3                   3—5 = —2                4
        16                  16—6=  10               16
                                          Total score 21

    Example  2.  Two candidates show the following performances.
Is one better than the other? What confidence is there in the selection?

    Candidate A
              Bottle Missing                Replaced in position
                    3                             1
                   16                            12
                    8                            12
                   12                            15

    Candidate B
                   16                            13
                   12                            15
                    3                             3
                    8                          .  10

    A's score                                     Score
                 3—1 =2                       4
               16—12 =4                      16
                8—13 = —5                      16
               12—15=—3                       9
                                                 45

    B's score
                                                 Score
               16—13 =3                       9
               12—15 = —3                       9
                 3—3 =0                       0
                8—10 = —2                      _4_
                                                 22
    A—B = 45—22 = 23

    Therefore B scored better than A. From the significance table
 (Table 2), this could have been due to chance alone 20% of the time.
Therefore, we have a confidence of 80% in our selection of B over A.
If we demand a confidence of, say, 90% before making a decision, then
we cannot  rule  out A as a possible  panel member before further
testing.
SELECTION OF JUDGES                                     11

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  THE MULTI-COMPONENT ODOR IDENTIFICATION
                            TEST

    This test presents three mixtures to the  candidate. These mix-
tures contain, in sequence,  2, 3, and 4 odors out of a possible total
of 8 known standards.  The candidate is  told how many components
to look for, and is asked to  identify them.

    The following materials are recommended as standards:

    1.  Oil of cade (burnt)
    2.  Cassia (cinnamon)
    3.  Eucalyptus
    4.  Amyl acetate (banana)
    5.  Clove oil
    6.  Orange oil
    7.  Almond oil (benzaldehyde)
    8.  Vanillin or vanilla extract

    Instructions are given as follows: "You have in front of you eight
labeled common odors. They are  (state  which).  These will be your
reference standards and  you may smell them whenever  you wish.
Now, you will be given an  unknown odor sample. This sample con-
tains a mixture of two of the standard odors.  Write down on your
score sheet which two  odors are present in  the test sample." When
this test is finished,  repeat the instructions  but  state that the new
sample contains a mixture of three standards. Then repeat the instruc-
tions again for  the third test explaining that the sample  contains a
mixture of four odors.

    The multi-component odor identification test is scored  as follows:

    Step  1. Administer the same test sequence, consisting  of three
tests, to each candidate.

        Test 1.  Two components

        Test 2.  Three components

        Test 3.  Four components

    Step  2.  Calculate the score of each  individual candidate accord-
ing to the following procedure.

m A  ,         / Number correct  \ 2          / Number correct \ z
Total score = (     in tegt 1     )       +    \     in test 2   )

                .     / Number correct \ 2
               ~*~     \    in test 3    /

    Step  3.  Refer to Table 3 to determine which  differences between
scores are significant.
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   TABLE  3 — SIGNIFICANCE OF  DIFFERENCES BETWEEN
           SCORES IN MULTI-COMPONENT ODOR
                    IDENTIFICATION TEST

       Difference between                 Probability that at least
        scores of any two                 this difference could have
           candidates                    been obtained by chance

                6                                25%
                7                                20%
                8                                15%
                9                                10%
               11                                 5%
               15                                 1%

  Example 1.  Candidates A and B scored as follows in  the multi-
component  odor identification test. Are the scores significantly dif-
ferent?
                                      Number Correct
    Test                  Candidate A               Candidate B
      1                         20
      2                         31
      3                         1                       4
    Score of A = 22 + 32 + I2 = 14
    Score of B = O2 -+- I2 + 42 = 17

    Difference = 3. The probability that  this difference  could have
been obtained by chance is greater than 25%. Therefore, we do not
attach any significance to this  difference, and the  two candidates
should not be differentiated from each other.

    Example 2.  Choose the best four candidates from the following:
      Test      Number correct obtained by each candidate.
                ABCDEFGHI
        1       021110202
        2       332010113
        3       424134023

    The scores are computed on the basis of the sum of the squares
of the correct answer and are then listed in order of magnitude. The
order is
                  Candidate               Score
                      A                    25
                       I                     22
                       C                    21
                       B                    17
                      F                    16
                      E                    11
                    G,H                     5
SELECTION OF JUDGES                                     13

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    Now, referring to Table 3, we can say with a confidence of 80%
that any candidates whose scores differ by no more than 7 points are
considered "equal."  By this criterion of confidence, candidates A, I,
and C could be considered to be equal and could be selected for the
panel.  Candidate B  differs from Candidate A by more than 7 points
and is  therefore ruled  out at this confidence level.  At a confidence
level of  90%, however, which implies  a lower probability  (10%)
that the observed differences of scores could have been obtained by
chance, we could have selected all of the candidates except the last
three.

      DEMONSTRATION OF SATISFACTORY  TEST
                         BEHAVIOR

    During  the  phases of candidate selection,  the  panel  leader  or
moderator should be attentive to various aspects of the candidates'
test behavior.  These aspects are:

    Speed.  The best behavior is purposeful and deliberate, neither
    excessively hasty nor slow.

    Interest level. The candidate should feel challenged and moti-
    vated. Candidates who find the work distasteful or uncomfortable
    should not be selected.

    Domination.  In group testing, the candidate should  be helpful
    when asked, but should not try to push his or her opinions on
    others.

    Independence. The candidate should be willing to consider the
    suggestions  of others,  but should  not  be  influenced to change
    score against his own judgment.

    Honesty.  Candidates  who  try  (successfully or  not) to  decode
    labels or peek under bottles should be rejected.

    The panel leader should observe the candidates' behavior in these
matters carefully but  unobtrusively. No specific numerical scoring
system is recommended; the leader should rely on his own judgment
with regard  to the sensitive question of whether to reject, on the basis
of poor test  behavior, any otherwise acceptable candidates.
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   THE TRAINING OF JUDGES FOR DIESEL

              EXHAUST ODOR STUDIES

    Training  should  be  scheduled according to the following  pro-
cedure.

    1.  Improve the performance of the judges in the same tests that
were administered for panel selection.  (Estimated time: 3-4 days).

    2.  Expose the judges to diesel exhaust under the conditions to
be used in the testing, under conditions of random ambient air dilu-
tion, to diesel fuel,  and to components of diesel exhaust condensate if
such are available. Discuss the four diesel odor descriptors (see Ap-
pendix 3) during each of these exposures.  (Estimated time: 2-3 days).

    3.  Introduce the judges to the kit of diesel odor reference stand-
ards. Explain how the standards will be used in measuring intensity
and  quality of diesel exhaust odor.   Train the panel members in
recognizing individual samples in  the  kit and in recognizing multi-
component samples. Establish minimum requirements for these tasks.
During this training, intersperse exercises that relate the diesel quality
standards to the sensory quality of diesel exhausts.  (Estimated time:
1-2 weeks).

    4.  Eliminate panel members as necessary in phases A, B, and C
for reasons of poor performance or motivation,  emotional problems,
excessive domination or dependence, or other difficulties apparent to
the moderator.

    5.  The panel  may now operate according to whatever experi-
mental  design is adopted as  the  original  research  program.  The
continued conduct of the work will, in effect, continue the training
of the panel. The  panel members should be checked  periodically to
insure  that the level of the performance with the kit components
obtained in phase 3 is maintained.

    Some of these phases of panel training are considered in more
detail in the following sections.


      INITIAL IMPROVEMENT OF PERFORMANCE

    The tests used for the  selection  of panel  members  should be
repeated, with one important  difference.  In training, no  errors are
ignored. As soon as  a trainee  or group of trainees scores a test, the
correct  answers  are disclosed;  the trainee repeats the exercise with
attention focused on elimination of the error,  with the help of the
leader.

     Example 1.

     Trainee: "I  detect eucalyptus, banana, clove,  and cinnamon in
this mixture."
TRAINING OF  JUDGES                                     15

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    Leader: "The mixture contains eucalyptus, banana, almond, and
cinnamon.  That means you reversed  clove and almond. Refer to the
almond and clove standards and recheck them and then smell your
mixture again."

    (Note  — The leader must not be deprecatory.  Say "reversed"
to express  the facts, not "confused" or "made an error" or "goofed"
to express disapproval.)

    Trainee: "Well, that almond is overpowered by the other odors.
It didn't come through for a while."

    Leader: "That's all right, it may happen that way. A four-com-
ponent mixture is a difficult task. Focus your attention on one com-
ponent at a time, take only short sniffs so you don't get fatigued, and
refer to the standards whenever you have to."

    During training, allow trainees to work together and help each
other by suggestions and exchange of comments and samples.  Keep
records of the trainees' progress.

    Training should be continued until there is a noticeable levelling-
off in  performance.  Prolonged continuation  of  training on known
mixtures is wasteful, because the diesel work will involve new ma-
terials and, of necessity, new training.

    An important aspect of training, and, later, of panel utilization is
the question of whether the panel should work on an individual or on
a group basis.  The individual basis eliminates social  influences; each
panelist's score is purely his own judgment. The group basis allows
for cooperative suggestions that will call  a  panelist's  attention to
something  that he himself senses only after his attention is properly
focused. The decision between the two methods is best made on  a
statistical basis. It will be appropriate to use the t-test to determine
whether or not the difference between the average panel scores
obtained on an individual and on a group basis is significant.


            EXPOSURE TO DIESEL EXHAUST

    The panel  members must be  exposed to diesel exhaust under
various conditions that are likely to be experienced in the proposed
testing program and also under typical  conditions expected on  the
street or highway. The panelists should also be exposed to diesel fuel
and/or fuel components, diesel exhaust condensate, and other relevant
odor sources. Explain to the panel members  that the quality of an
odor can be described in terms of quality components. The explana-
tion can be an expansion of remarks such as the following:

    "You have identified the components of mixtures of two, three,
or four odorants in the tests you have been conducting during the last
few days. This identification is also a description of odor quality.  You
may say that the odor of a given sample is a mixture of lemon and
vanilla. This statement describes  the quality of the odor mixture,
16                                      TRAINING OF JUDGES

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just as the same statement would be a description of flavor if the
sample were a piece of cake. We are going to describe diesel exhaust
in terms of four qualities:

     1.  Burnt/smoky.  This is the quality in which diesel exhaust is
related to the odors of other products of burning or combustion.

     2.  Oily.  This  quality is the oiliness related to the presence of
the odor of the heavy components of unburned fuel.

     3.  Pungent/acid.  This is the quality associated with pungency
in high concentration, gradually changing to an acid or sour quality
with greater dilution.

     4.  Aldehydic/aromatic. This is the quality related to what may
be thought of as the "fragrant" aspect of diesel exhaust.  It may also
be thought of, in most instances, as that  quality not represented by
smokiness, oiliness, or pungency."

      LEARNING THE DIESEL ODOR STANDARDS

     (Refer to Appendix B for details of the composition and prepara-
tion of the diesel odor kit.)

     The following  introductory remarks may be appropriate:

     "You will be given a kit of standard odors to which you will refer
in making your odor judgments. Standard odors D-l through D-12
represent the intensity levels of diesel exhaust odor, without regard
to quality.  Standards B-l to B-4 represent four intensity  levels of
burnt odor; O-l to O-4 represent intensity levels of oily odor.  (The
moderator at this point should explain the entire kit.)  Before  using
these standard odors to measure diesel exhaust, it will be necessary
for each of you to learn the various standards and to get some famil-
iarity with mixtures of the standards."

     The training for recognition of  odor standards should now pro-
ceed along the following lines.
                                                                 \
     1.  The judges should be trained in the intensity levels of the
D-l  to D-12 series.  Judges should be able to identify any unknown
sample to within  ± 1 or 2 intensity levels.

     2.  The judges should learn each of the quality components at
the "extreme" concentration (B-4, O-4, P-4, and A-4). They should
then learn to identify each intensity  of each quality, 16 bottles in all.
They should be  able to  identify all  unknowns as  to quality and
intensity about 90% of the time.

     3.  The judges should learn to identify two- and three-component
mixtures, until performance levels off.  They should reach a level at
which they identify mixtures correctly about 80% of the time. The
compositions of standard mixtures are shown in Table 4 and  5. Prob-
abilities of obtaining correct identifications  by chance are shown in
Table 6.
TRAINING  OF  JUDGES                                      17

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       TABLE 4 — COMPOSITION OF  COMPONENTS
            FOR ODOR STANDARD MIXTURES

   Quality       Code (t= training)     Composition
   Burnt               B-t       B-4 (See Appendix 3)
   Oily                 O-t       100% octylbenzene
   Pungent             P-t       P-4
   Aldehydic            A-t       1 % A in mineral oil

TABLE 5 — COMPOSITION OF ODOR STANDARD MIXTURES
                     FOR TRAINING
  Number of
  Components   Code (t = training)      Composition
 AB-n
 AO-t
 AP-t
 BO-t
 BP-t
 OP-tJ

ABO-tl
ABP-t
                                  1 : 1 mixtures of the
                                  solutions of Table 4.
                                  About % to 1 ml of
                                  solution is placed in a wad
                                  of cotton in a plastic
                                  squeeze bottle.
                                  1:1:1 mixtures as above.
                 BOP-t-

       4        ABOP-t           1:1:1:1 mixture as above.

  TABLE 6 — PROBABILITY OF CORRECT IDENTIFICATION
      OF TRAINING STANDARDS BY CHANCE ALONE

         Number of components
         stated to be in mixture         Probability per test
                  1                        1/4
                  2                        1/6
                  3                        1/4
             Not disclosed                   1/15
18                                  TRAINING OF JUDGES

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                ACKNOWLEDGMENTS

    The following chemists participated in the development  of the
odor standards: Louis Reckner, Robert Squires, and Z. Tomaras, all of
the Scott Research  Laboratories; Stanley Mehlman  and Elizabeth
Wolf, both of the City University of New York; and Jonathan Turk,
of Brown University.

    The statistical calculations were derived by Janet T, Wittes of the
Department of Statistics, Harvard University.
                              19

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    APPENDIX  A:   CONCENTRATIONS  OF

   ODOROUS  VAPORS  IN TEST  CHAMBERS

    Odor test chambers are used either for evaluation of odor-reduc-
ing devices or to provide odor-free environments in which a jury can
measure the odors of materials, products, or foods. It is important to
consider the factors that determine the changing or equilibrium con-
centrations in such chambers.

   Processes that tend to increase  the  concentration of  odorous
vapors are:

(a) the generation  of vapor within (or injection into) the space,

(b) the introduction of  vapor by replacement  of chamber air by
    ventilation or infiltration with outdoor air of higher vapor con-
    centration.

    Processes that  tend  to decrease the concentration of  odorous
vapor are:

(a) the treatment  of the chamber air  by a vapor-reducing device
    (e.g., activated carbon recirculator),

(b) the removal of vapor by replacement  of chamber air by ventila-
    tion or infiltration with outdoor air of lower vapor concentration.

    The concentration of odorous vapor in a chamber will approach
an equilibrium value in which the rates of vapor-reducing and vapor-
increasing processes are equal. If it  is  assumed that air introduced
into the chamber by ventilation,  infiltration, or recirculation through
a treatment device is completely  and instantaneously mixed with the
chamber air, then the concentration of vapors at any time and at
equilibrium are given by  the general equations:
       -(Q, + EQr)t/V
C = C0e
                                 / CA + G \
                                 V Qi + EQr /
            |
                           + G
                       Qt 4- EQr
   SPECIAL CASES  OF THE GENERAL EQUATIONS

Consider the following possibilities:
    (a) Ventilation air is pure. (Ct = 0)
    (b) No vapor is being generated or injected.
        (G = 0)
 APPENDIX A                                              21

-------
    (c) The vapor reducing device is 100% efficient.
        (E = 1 and Cr = 0)
    (d) The chamber is originally pure. (C0 = 0)
    (e) The room is tight.  (Q, = 0)
    (f) Combination of (a) and (b)
    (g) Combination of  (a) and (c)
    (h) Combination of (b) and (e)
    (i) Combination of  (a), (b), and (c)
For each possibility (a) through (i), the equation for the vapor con-
centration at any time (C) or at equilibrium (Cw ) is derived directly
from the general equations:
    (a) C, = 0
            —(Q, + EQr)t/V       G
      C = Cne              ~r f o. _|_ EQr)
            0
             f  _~(Qi + EQr)t/V 1
                    * (Q, + EQr)
    (b)G = 0
                    EQr)t/V  .     C
-------
    (e)Q1=0
        —EQtt/V       G   /   —EQrt/V\
  C = C0e         +   EQr  V 1 — e      /

and                      C. = G/EQr

    (f) Combination of (a)  and (b). Ct and G = 0
        —(Qt + EQr)t/V
  C = C0e
and                        c  — 0
                             CO
    (g) Combination of (a) and (c). Cj = 0, E = 1, and Cr= 0
     — (Qi + Qr)t/V
     C0e
       G          — (Qi + Qr)t/V
and                  C — _ - _
                       °°   Qt + Qr

    (h) Combination of (b) and (e). G == 0, and Qi = 0
                             — EQrt/V
                      C = C0e
and
    (i) Combination of (a), (b), and (c). C| = 0, G = 0,
E= 1, andCr=0
                       — (Qi + Qp)t/V
                C=C0e
and
                           C_=0
                             oo
      EXPRESSION IN TERMS OF AIR  CHANGES

    An air change is the addition to the chamber of a volume of air
equal to the volume of the chamber.  Then the number  (N)  of air
changes (dimensionless) per unit time is given by:

                        N/t = Q/V, or
                          N = Qt/V
                     MIXING FACTOR
    In any expression of the general form e"0^ or  e~N, a mixing
factor, m, may be applied to account for the fact that  dilution of air
is not instantaneous, and that concentration fall-off rates are actually
smaller than the ideal values given by the equations developed here.
Brief2 suggests that m commonly ranges between 1/3 and 1/10.
APPENDIX A                                               23

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                    SENSORY TESTING

    The efficiency of a vapor-reducing device may be measured by
sensory methods that obviate the need for determination of material
concentrations.  If we select a sealed chamber in which no  odor is
being generated, then the ratio of concentrations C1/C2 corresponding
to any two times tx and t2 during the operation of the device is

                                    (t-j — t,)


    It is possible to measure the ratio of two supra-threshold concen-
trations of odorous vapor CJC2 by either a dilution or a matching
technique. Let

 p__  Volume of air sample diluted to threshold
            Volume of original air sample       =  / t

Then, the ratio of P values for any two concentrations CJCZ is:
                        C2/Ct '

                         PJP,
We may therefore write
          (EQ.ni/V) (t, — t,)
  Px/Pa = e
and
             Iog10 P./Pa = 0.434 (EQrm/V) (t2 — t
Solving for E,
                    2.303 Iog10
                               — tT)

    The latter equation tells us that for a room of known volume and
air mixing characteristics,  it is  possible, by  sensory determination
odor hi the room at different times, to measure the efficiency of a
vapor-reduction device operating within the room.

    Example:  In a lOOO-cu.-ft. sealed room, 50 cfm of air is recircu-
lated by an air purifier of 60%  efficiency.  The mixing factor in the
room is %. Some diesel exhaust vapor is spilled into the room.  How
long must the air purifier operate if the vapor  concentration in the
room is to be reduced by 90%?
    Solution: C, = Cx — 0.90^ and Ct/Ca = 10

                  2.303^(^/02         2.303 log 10
                     EQ,m/V        0.60 x 50 x %/1000

                    = 230 min., or 3 hr. 50 min.
24                                                APPENDIX A

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                          NOTATION

   V  = Volume of chamber
   t   = time
   C  = concentration of vapor in chamber at any time
   C0 = initial concentration of vapor in chamber
   Cw = concentration of vapor in chamber at equilibrium
   C,  = concentration of vapor in ventilation or infiltration air
   Cr = concentration of vapor delivered by the air treatment device
   E  = efficiency of vapor reduction by the air treatment device
   Q, = volume rate of ventilation or infiltration
   Qr = volume rate of air delivery by the air treatment device
   G  = quantity rate of generation of vapor within
         (or injected into) chamber
   N  = number of air changes
   m  = mixing factor
  1.  A. Turk, Measurements of Odorous Vapors In Test Chambers: Theo-
retical. ASHRAE J., Oct. 1963.
  2.  R. S. Brief, Simple Way to Determine Air Contaminants, Air Engineer-
ing, Vol. 2, p. 39 (1960).
 APPENDIX A                                                 25

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  APPENDIX B:   SENSORY  STANDARDS FOR

         DIESEL EXHAUST  ODOR STUDY

    This Appendix describes the composition and method of prepara-
tion of sensory standards for diesel exhaust odor study. The stand-
ards are designed to serve as sensory references for (a) the intensity
of diesel exhaust odor, without regard to the quality of the odor, (b)
the quality of diesel exhaust odor, expressed in terms of the intensities
of each of four odor quality descriptors, and (c) the intensity of odor-
modifying agents that are  designed to improve diesel exhaust odor
by odor masking or odor counteraction.

     The intensities of the individual odor qualities, taken together,
constitute  a "quality-intensity profile," or "QI profile." The profile is
not designed so that the  sum of its intensity scores should be related
to the overall diesel  exhaust odor intensity.

    Descriptors are  used to designate diesel exhaust odor quality.

    The descriptors  are:

        Name                                  Code

        Burnt/smoky                           B
        Oily                                   O
        Pungent/acid                           P
        Aldehydic/aromatic                     A
        Masking                               M


                    BURNT/SMOKY  (B)

    Burnt quality or smokiness is a  typical odor component of the
products of combustion of organic matter. There is considerable vari-
ation in the quality  of burnt odors, however, among different condi-
tions of combustion, different materials being burned, and  different
states of molecular or aerosol aggregation of the airborne combustion
products.  Many of  the  primary combustion products  are  unstable
and therefore unsuitable for use as sensory reference  standards. The
chemical makeup of materials that have a burnt odor includes prod-
ucts of decomposition and partial oxidation.  Oil of cade (juniper tar)
is included in the B  standard because this oil has a typical  burnt odor
and is readily available from commercial sources.  Guaiacol and car-
vacrol  impart the  phenolic odor component that  is contributed to
some extent by the oxidation of benzenoid aromatic matter. Acetylene
dicarboxylic acid is a commercially available chemical whose odor
somewhat resembles that of a dilute mixture of carbon suboxide in
air.  Carbon suboxide is a likely product of  partial oxidation that
contributes  to burnt odor. Benzyl  benzoate  is  an almost odorless
diluent that solubilizes the other components.
APPENDIX B                                               27

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Composition of B
                                     Percent by weight
        Component             including           excluding
       	solvent	solvent

        Oil of cade                16.8                84.3
        (Juniper tar)
        Guaiacol                   0.2
        Carvacrol                   0.9
        Acetylene dicarboxylic acid  2.1
        Benzyl benzoate           80.0
                                 100.0
                                            (solvent/odor ant, 4:1)
Intensity series (diluent: as noted)

                            Concentration (B/B -|- diluent)
Odor intensity
Slight
Moderate
Strong
Extreme
Code
B-l
B-2
B-3
B-4
Diluent
min. oil
min. oil
min. oil
benz. ben.
Fract.
1/720
1/180
1/45
1/4
Decimal
0.00319
0.00556
0.0222
0.25
%
0.139
0.556
2.22
25.
Procedure
    Make up the stock mixture B.
    To make B-4, mix 1 part of B with 3 parts of diluent.
    To make B-3, mix 1 part of B-4 with 44 parts of diluent.
    To make B-2, mix 1 part of B-3 with 3 parts of diluent.
    To make B-l, mix 1 part of B-2 with 3 parts of diluent.

    Notes: (a) The dilutions can be made on a volume basis without
               introducing any significant error.
           (b) Stock solution B  should be shaken before dilutions
               are made to bring into suspension any component of
                the oil of cade that might have settled.
            (c)  Note the change in diluent between B-4 and B-3.


                           OILY  (O)

    Oiliness is  an odor  quality  generally  associated with organic
 chemicals whose molecular.structure is characterized by long satu-
 rated  hydrocarbon chains. Among  materials of plant  origin such
 substances are typically  esters of long-chain  fatty acids.  In diesei
 exhaust, oily quality  is believed to be associated with the presence of
 high-boiling-point components of unburned fuel, in the boiling range
 approximately 300° C (1  atm).  The most satisfactory standard found
 to represent this odor quality is n-octylbenzene.
 28                                                 APPENDIX B

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Composition of O

    n-Octylbenzene, 100%

Intensity series (diluent: mineral oil)

                            Concentration, O/(O -\- diluent)
Odor intensity
Slight
Moderate
Strong
Extreme
Code
O-l
0-2
O-3
0-4
Expon.
2~7
2-s
2~3
2~l
Fract.
1/128
1/32
1/8
1/2
Decimal
0.0078
0.0313
0.125
0.5
%
0.78
3.13
12.5
50.
Procedure
    The stock material O is pure n-octylbenzene.
    To make O-4, mix 1 part of O with 1 part of diluent.
    To make O-3, mix 1 part of O-4 with 3 parts of diluent.
    To make O-2, mix 1 part of O-3 with 3 parts of diluent.
    To make O-l, mix 1 part of O-2 with 3 parts of diluent.

    Note: (a) The  dilutions  can be made on a volume basis without
              introducing  any significant error.


                     PUNGENT/ACID (P)

    Diesel exhaust in high concentration  can be  perceived  as an
irritant.  The word  "irritant" is used  here to denote a substance that
can be detected by  the common chemical sense, as distinguished from
the specific olfactory sense.  Such irritants are said to have a "pun-
gent" quality. This type  of  common chemical sensation can coexist
with odor.  Thus, a  concentrated mixture of butyric acid vapor in air
is both pungent and odorous. As the  mixture is diluted, the common
chemical irritation  diminishes and then disappears  at concentrations
at which odor still  persists.  The sensation is then no longer said to
be pungent; instead, it is described as  "acid," or "sour." The existence
of pungent, acid components in diesel exhausts is evidenced by (a) the
interpretation of  infrared  spectra by Scott  Research Laboratories to
indicate  the  presence of  organic  acid  (carboxyl function), (b) the
sensory identification of "sour" substances among the column chroma-
tographic fractions  of diesel exhaust obtained by Scott Research Lab-
oratories, and (c)  the pungency experienced  by direct exposure to
concentrated diesel exhaust.

    The character of "sourness" or "acid odor" (as distinguished from
pungency) varies among  different sources.  Butyric and valeric acid
odors are characterized by sour odor qualities typical of rancidifica-
tion of organic matter. An acidic odor quality more closely related
to combustion products  is associated with organic acids that have
olefinic or acetylenic unsaturation.
APPENDIX B                                                 29

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Composition of P
     Component               Percent by weight

  Crotonic acid                        3.3
  Propiolic acid                       2.9
  Benzyl benzoate                    93.8
                                     100.0
Intensity series (diluent: mineral oil)

                           Concentration, P/(Pj-f- diluent)
Odor intensity
Slight
Moderate
Strong
Extreme
Code
P-l
P-2
P-3
P-4
Fract.
1/720
1/180
1/60
1/20
Decimal
0.0014
0.0055
0.0167
0.05
%
0.14
0.55
1.67
5.0
Procedure
    Make up  the  stock solution  P.  The mixture will have to be
warmed slightly to bring the components into solution.  Allow the
solution to cool to  ambient temperature.

    To make P-4, mix 1 part of P with 19 parts of diluent.
    To make P-3, mix 1 part of P-4 with 2 parts of diluent.
    To make P-2, mix 1 part of P-3 with 2 parts of diluent.
    To make P-l, mix 1 part of P-2 with 3 parts of diluent.

    Note: (a)  The dilutions can be made on a volume basis without
              introducing any significant  error.
          (b)  The components of P-4 may have to be warmed to
              bring them into solution.


               ALDEHYDIC/AROMATIC  (A)

    Aldehydes are known to exist as components of diesel exhaust.
Some of the column chromatographic fractions of diesel exhaust ob-
tained by Scott Research Laboratories were characterized as having
"sweet" or "spicy" odors.  A mixture used  at Scott Research Lab-
oratories for setting up odor intensity  ratings of diluted diesel exhaust
contained heptaldehyde as  the major component.   These circum-
stances, taken  together, support the selection of a quality description
of diesel exhaust odor that reflects aldehydic and other highly odorous,
somewhat fragrant components. The intensity series  that consists of
these pervasive odorants is represented by comparatively dilute solu-
tions.
30                                                APPENDIX B

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 Composition of A
                 Component             Percent by weight
               n-Butylbenzene
               sec-Butylbenzene
               p-Cymene
               Heptaldehyde
               Nonaldehyde
               Salicylaldehyde
               Cinnamic aldehyde
               alpha-Methylcinnamic aldehyde
               p-Tolyl aldehyde
 Intensity series (diluent: mineral oil)

                            Concentration, A/(A -|- diluent)
Odor intensity
Slight
Moderate
Strong
Extreme
Code
A-l
A-2
A-3
A-4
Expon.
2-ie
2-1*
2~12
2~io
Fract.
1/65536
1/16384
1/4096
1/1024
Decimal
0.00001525
0.0000610
0.000244
0.000976
%
0.0015
0.0061
0.0244
0.0976
ppm
15
61
244
976
Preparation

    Make up the stock solution A. The components are highly odorous
and should be handled in the fume hood.
    To make A-4, calibrate a pipet or dropper in mg/drop of stock
solution A. Pipet a measured quantity of A into a flask.  Add mineral
oil in the ratio 1.02 g mineral oil/mg A.  Shake the mixture to dissolve
the components.

    To make A-3, mix 1 part of A-4 with 3 parts of diluent.
    To make A-2, mix 1 part of A-3 with 3 parts of diluent.
    To make A-l, mix 1 part of A-2 with 3 parts of diluent.

    Note: (a) The dilutions can be made on a volume basis without
              introducing any significant error.

                       MASKING (M)

    Odor-modifying agents are designed to  improve objectionable
odors by  admixture with another vapor that will change the malodor
quality (masking  action) and/or reduce the malodor intensity (odor-
counteracting action). Agents of this type differ among manufacturers
and are proprietary. When such agents are used for modification of
diesel odor it will be helpful to have a general  "masking" standard
to use as  a quality reference. Such a standard should contain compo-
APPENDIX B                                                31

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nents of the type likely to resemble the composition of common diesel
masking agents or to be associated in the experience of panel members
with commercial products that contain mixtures of industrial essential
oils.

Composition of M

                Component             Percent by weight

               Oil of wintergreen              10
               Terpineol                       20
               Cedrene                        20
               Bornyl acetate                  30
               Phellandrene                   20

Intensity series (diluent: mineral oil)
                           Concentration, M/(M -f- diluent)
Odor intensity
Slight
Moderate
Strong
Extreme
Code
M-l
M-2
M-3
M-4
Expon.
2-w
2-13
2~io
2~-
Fract.
1/65536
1/8192
1/1024
1/128
Decimal
0.00001525
0.000122
0.000976
0.00781
%
0.0015
0.0122
0.0976
0.781
ppm
15
122
976

Preparation

     Make up the stock solution M.  The components are highly odor-
ous  and should be handled in the fume hood.

     To make M-4, calibrate a pipet or dropper in mg/drop of stock
solution M.  Pipet a measured quantity of M into a flask. Add mineral
oil in the ratio 0.127 g mineral oil/mg M. Shake the mixture to  dis-
solve the components.

     To make M-3, mix 1 part of M-4 with 7 parts of diluent.
     To make M-2, mix 1 part of M-3 with 7 parts of diluent.
     To make M-l, mix 1 part of M-2 with 7 parts of diluent.

     Note:  (a) The dilutions  can be made on a volume basis without
               introducing any significant error.

                          DIESEL  (D)

     As stated earlier, the intensity of diesel exhaust odor may be
measured without  regard to the quality of the odor.  The intensity
reference standards, therefore, could consist of a dilution scale of any
convenient odorant. It is considered likely, however, that panel mem-
bers will become proficient in QI odor profile work more easily if the
overall intensity reference standard is related to  the individual odor
quality standards.
 32                                                APPENDIX B

-------
Composition of D
          Component
Percent by volume
              B-4
              0-4
              A-4
Intensity series (diluent: mineral oil)
                   	Concentration, D/(D -f diluent)	
Odor intensity  Code Expon.   Fract.     Decimal      %    ppm

Slight


Moderate


Strong


Extreme

D-l
D-2
D-3
D-4
D-5
D-6
D-7
D-8
D-9
D-10
D-ll
D-12
2-"
2-io
2-9
2-8
2-7
2-6
2-5
2~*
2-3
2^
2-i
2-o
1/2048
1/1024
1/512
1/256
1/128
1/64
1/32
1/16
1/8
1/4
1/2
1
0.000488
0.000976
0.00195
0.00391
0.00781
0.0156
0.0313
0.0625
0.125
0.25
0.5
1
0.0488
0.0976
0.195
0.391
0.781
1.56
3.13
6.25
12.5
25.
50.
100.
488
976










Procedure
    Make up the stock solution D.
    D-12 is identical with stock solution D.
    To make D-ll, mix 1 part of D-12 with 1 part of diluent.
    To make D-10, mix 1 part of D-ll with 1 part of diluent.
    Continue in this manner until D-l is prepared.
    Notes:  (a) The dilutions  can be made on a volume basis without
               introducing any significant error.
           (b) Stock solution B should be shaken before dilutions
               are made to bring into suspension any component of
               the oil of cade that might have settled down.

        SOURCES AND PURITY OF  CHEMICALS

    All of the chemicals used must be pure enough that any impur-
ities present do not make a detectable contribution to odor.  For
highly odorous chemicals,  such  as aldehydes,  this  requirement nor-
mally poses no problem.

    A good odorless mineral oil is Primol 325 available from Humble
Oil & Refining Company, Hutchinson River Parkway, Pelham, New
York.
APPENDIX B
                     33

-------
    The benzyl benzoate should not have any of the cherry or al-
mond odor that may be associated with the presence of some benzal-
dehyde impurity.  Satisfactory grades are available from Mallinkrodt
Chemical and from the Matheson Company.

    The octyl benzene must not emit any of the sulfur  odor that is
sometimes associated with inferior samples. A satisfactory grade may
be purchased  from the  Humphrey Chemical Company,  in North
Haven, Connecticut.

    Acetylenic compounds are available from Farchan Research Lab-
oratories, Willoughby, Ohio.

                        CONTAINERS

    25 ml of each odorant reference solution is placed in a labeled
4-oz polyethylene squeeze bottle, fitted with a screw cap having  a
conical polyethylene liner.

    The entire kit comprises 32 bottles (12 of the intensity series and
4 each of the 5 components of the QI profile, including the masking
standards).  These bottles should be arranged in  a metal rack in  a
metal box that is provided with an internal activated-carbon panel to
keep the atmosphere in the box odor-free. Porous materials of con-
struction like  wood or cardboard should be avoided because  they
absorb and  retain odor.  The activated carbon should  be  granular
material of the type commonly used for air purification.
34                                                APPENDIX B

-------
 APPENDIX  C:   STATISTICAL  DERIVATIONS

   STATISTICAL DERIVATION OF TRIANGLE  TEST
                       SELECTIONS

    We have a number of candidates who take m triangle tests each.
On the basis of the number of correct answers, we wish to choose
the "best" candidates. It is assumed (a) that the candidates act inde-
pendently of each other, and (b) that the test has been demonstrated
to them beforehand so  that they are not learning during  the test
sequence. Each test is therefore independent of the other tests taken
by the same candidate.

    Now, if a candidate answers purely by guesswork, the chance of
getting a correct answer on any single  test is 1/3.  The probability of
getting x correct answers out of m is  expressed by the probabilities
of the binomial distribution:

         P'~
                xl (mx)!
             where px = probability that a candidate would give
                        x correct answers.
                  m = number of triangle tests given.
                   x = number of correct answers.

    Suppose we have two candidates, one who has x correct answers
and one who has y, and we want to know whether the difference be-
tween the two is significant.  We therefore want the distribution of
/x-y/. According to "distribution theory" in probability, x and y are
identically, independently distributed  binomial  random  variables,
where

    P'~ x! (m-x)!  ('/3)'(2/3)"
    The expected value (E = expectation) of any function f(x) is
denned as
                m
    E(f(x))=  ^   Plf(x)
    By convention, we choose f (x) = t1, where t is a dummy vari-
able.
    Then,
              m
                                 These are called the
                                 "generating functions'
    E(tx) =   2E  t'p,   and
              x = 0
              m
              x = 0
                                 of px and py.
 APPENDIX C                                              35

-------
    Now, we want P(x-y), the probability distribution of (x-y).

    E (t^T)  = E (tx) E  (t~y)

             m              m

                           x = 0

                 m    „      m!
                                                    ,
                                                    '
                                                .
                                               x.
                                                                 (2/3)'
        and similarly,
                        m
                        1     2
                   = (-— -(- -^
                       Ot    O
        Then,
                1       2
              (— - t -j — 5— )m
                t>       O
                                           (by binominal expansion)
                                                       -)m~y
                               ! '   3t '     3


                               (by binominal expansion)
[
                        9
                                    )
                                                     This is the generating
                                                     function of P(x.y).
            To find the distribution it is necessary to expand the generating
        function, gather like terms, and consider two competing candidates, A
        and B, whose respective scores are x and y.  The probability that, by
        chance  alone, the difference  between the two scores is 2  (or  that
        x — y = z) is the coefficient of the term hi t. Now, if two candidates
        take m  triangle tests each, the maximum difference between scores is
        -j- m or — m. The probability that, by chance alone, the difference
        between the scores is z, or x — y = z, is the coefficient of the term in t.
        o    (there are no tests)
        Let m

        Then,
                and P°   =1   (Probability is 1 that score is tied)

        Let m = 1   (one test is carried out)
36
                                                            APPENDIX C

-------
Then,
                 J
andP_,
           _2_
           ~9~
                   2                         2
or, the chances are — =— that A will win over B, — — — that B will win
over
       and
   9

that A and B will tie.
                                             y
Let m

Then,
                               +
Therefore,

^^   A


    P., =
                 81
    P_2 -
                      -
                        +
            20
            81
             8/729
            60/729
     '_!  = 174/729
    P0  = 245/729
    Px  = 174/729
    P2  =  60/729
    P3  =   8/729

By computer calculations for
33
81
 20
~31
                                                         81
                                                             t2
    P.4 =
    P_3 =
    P.2 =
    P., =
    P0  =
    Pt  =
    P2  =»
    P   =
             16/6561
            160/6561
            664/6561
           1480/6561
           1921/6561
           1480/6561
            664/6561
            160/6561
             16/6561
APPENDIX C
                                                             37

-------
for m = 5
    P_5 =    32/59,049
    P.4 =   400/59,049
    P_3 = 2,160/59,049
    P.2 = 6,600/59,049
    P.J =12,570/59,049
    P0  = 15,525/59,049
    P,  = 12,570/59,049
    P2  =  6,600/59,049
    P3  =  2,160/59,049
    P4  =   400/59,049
    Ps  _    32/59,049

    Now, in a series of triangle tests taken by candidates A and B,
the distribution of the differences in correct scores Ix-yl tells us what
the probability is that any given difference in scores obtained by A
and B  is due to chance alone. These distributions appear in Tables
Cl and C2.

      TABLE Cl —TRIANGLE TESTS, DISTRIBUTION OF
                  DIFFERENCES IN SCORES

      Number of triangle
           tests, m                   Distribution of Plx-yl
0
1

2


3



4




P0
PO
"i
PO
P!
P2
PO
PI
P2
P3
Po
1^
n^J
in
~^j
_ i
= 5/9
= 4/9
= 33/81
= 40/81
— 8/81
= 245/729
= 348/729
= 120/729
= 16/729
= 1921/6561
= 2960/6561
= 1328/6561
= 320/6561
= 32/6561
                                        P0  = 15525/59049
                                        Px  = 25140/59049
                                        P2  = 13200/59049
                                        P3  = 4320/59049
                                        P4  =  800/59049
                                        P5  =   64/59049
 38                                                APPENDIX C

-------
               TABLE C2 — TRIANGLE TESTS,
          CUMULATIVE DISTRIBUTION FUNCTIONS

                                       Probability that the
                                      difference in scores of at
 Number of triangle                  least x — y would be obtained
tests, m
0 PO
1 PO
PI
2 P
PI
P2
3 P0
PI

PS'
4 pQ
PI

PS
P4
5 P0
PX
P2
PS
P*

Plx-yl
= 1
= i
= 4/9
= 1
= 48/81
= 8/81
== 1
= 484/729
= 136/729
= 16/729
= 1
= 4640/6561
= 1680/6561
= 352/6561
= 32/6561
= 1
= 43524/59049
= 18384/59049
= 5184/59049
= 864/59049
= 64/59049
by chance
1.00
1.00
0.44
1.00
0.59
0.099
1.00
0.66
0.19
0.022
1.00
0.71
0.25
0.051
0.0049
1.00
0.74
0.31
0.088
0.015
0.0011
alone
100%
100%
44%
100%
59%
9.9%
100%
66%
19%
2.2%
100%
71%
25%
5.1%
0.49%
100%
74%
31%
8.8%
1.5%
0.11%
 STATISTICAL DERIVATION OF INTENSITY RATING
                    TEST SELECTIONS

                       ASSUMPTIONS

    When two candidates replace  a  sample  at or near the correct
position, they are candidates who  will be considered for favorable
action and it is important to make  a good distinction between them.

    Candidates who replace the samples very far from the correct
position are not likely to be chosen and we  don't care much about
distinctions between "very bad" and "extremely bad."

    For example: correct position = 3
    Candidate A  Replaces sample in position 3
    Candidate B  Replaces sample in position 4
    Candidate C  Replaces sample in position 17
    Candidate D  Replaces sample in position 18
APPENDIX C                                              39

-------
Then A's score is slightly better than B's and we want to know how
reliable this difference is. Candidate C and D are both very poor and
we don't really care whether one is worse than the other.

                           SCORING

            Position of replaced          Score (the higher number
	bottle	is the worse score)

            Correct position                       0
            Correct position ±1                    1
            Correct position ±2                    4
            Correct position ±3                    9
            Correct position ± 4 or more            16

Each candidate must be given the same program; they must not com-
municate with each other.

	Test Number	Correct position of sample

               1                                3
               2                                8
               3                               12
               4                               16
            DISTRIBUTION OF POSSIBLE  SCORES:
Correct
Answer
3




Explanation:
Bottle
Position:
Possible
Scores
0
1
4
9
16


123456
Probability of
each score
1/20
2/20
2/20
1/20
14/20


789 	 20
Deviation from
correct location:   —2 —1   0 +1 +2  -}-3  +4 -f5 -j-6  etc.

Score              4   1   0    1   4   9   16  16   16 	  16

Number of ways of getting a score of 0 is  1 out of 20.
Number of ways of getting a score of 1 is  2 out of 20.
Number of ways of getting a score of 4 is  2 out of 20.
Number of ways of getting a score of 9 is  1 out of 20.
Number of ways of getting a score of 16 is 14 out of 20.
                                                  APPENDIX  C

-------
Possible
Correct Answer Scores
8, 12, or 16 0
1
4
9
16
Probability of
each score
1/20
2/20
2/20
2/20
13/20
Therefore, in the sum of the four tests, the lowest possible score (the
best) is 0; the highest possible score (the worst) is 64.
    Table C3  gives the probability distribution of scores  in the odor
intensity tests.

 TABLE  C3 — PROBABILITY DISTRIBUTION  FUNCTION AND
  CUMULATIVE DISTRIBUTION FUNCTION OF DIFFERENCE
 IN SCORES  OF TWO SUBJECTS ON ODOR-INTENSITY TEST
Difference
in score
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Probability of
Difference
0.0899
0.0289
0.0140
0.0467
0.0372
0.0374
0.0124
0.0754
0.0465
0.0274
0.0165
0.0191
0.0834
0.0123
0.0175
0.0822
0.0466
0.0119
0.0111
0.0333
0.0176
0.0096
0.0259
0.0214
0.0222
0,0051
0.0063
0.0292
Cumulative
Probability of
Difference
1.0000
0.9101
0.8812
0.8672
0.8205
0.7883
0.7459
0.7335
0.6581
0.6116
0.5842
0.5677
0.5486
0.4652
0.4529
0.4354
0.3532
0.3066
0.2947
0.2836
0.2502
0.2326
0.2230
0.1971
0.1757
0.1534
0.1483
0.1423
Nominal
Significance
Level


















0.30

0.25


0.20

0.15


APPENDIX C
41

-------
                 TABLE C3 — (Continued)
Difference
in score
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
Probability of
Difference
0.0156
0.0046
0.0164
0.0182
0.0062
0.0021
0.0073
0.0055
0.0033
0.0037
0.0040
0.0053
0.0024
0.0007
0.0038
0.0038
0.0012
0.0015
0.0023
0.0013
0.0004
0.0005
0.0005
0.0004
0.0003
0.0002
0.0004
0.0003
0.0001
0.0002
0.0002
0.0001
0.0001
0.0001
0.0001
0.0000
0.0000
Cumulative
Probability of
Difference
0.1131
0.0975
0.0929
0.0765
0.0583
0.0521
0.0500
0.0427
0.0372
0.0339
0.0302
0.0262
0.0209
0.0185
0.0178
0.0140
0.0102
0.0090
0.0075
0.0052
0.0039
0.0035
0.0030
0.0025
0.0021
0.0018
0.0016
0.0012
0.0009
0.0008
0.0006
0.0004
0.0003
0.0002
0.0001
0.0000
0.0000
Nominal
Significance
Level

0.10




0.05









0.01











0.001





0.0001


 STATISTICAL DERIVATION OF MULTICOMPONENT
      ODOR IDENTIFICATION TEST SELECTIONS

    A candidate is given eight known odor standards, A, B, C, D . . .
H. He is then asked to identify, in three successive tests, the compo-
nents of a two-component mixture, a two-component mixture, and a
four-component mixture.
42                                          APPENDIX C

-------
                 TWO-COMPONENT MIXTURE

    Let the two components be A and B.  The chances  of guessing
both correctly are:

                 1               1               1
                        X
                 8      ~      7     ~      56
         chance of guessing  guessing
              A first         B next
or
                 87             56
             guessing B      guessing
                first          A next

                              Total   =
                                             56
The chances of guessing only one correctly are:
                —    *     —    -      6
                 o      S^-      n
                               7             56

         chance of guessing        guessing
              A first        C, D, E, F, G, or H next

                 6              1              6
or             	    ~y     	    =
                 8      ^      7             56

      chance of guessing     guessing
     C, D, E, F, G, or H first    A next

Similary, chances of guessing only

            6                                12
            56                               56
                              Total    =     24
                                             56
The chances of getting none correct are
            6                        5                    30
                        X
            8^7                    56

   chances of guessing       chances of guessing
  C, D, E, F, G, or H first    C, D, E, F, G, or H next
                                                         KG
                                      Grand total
                                                         56

Three-component  mixture  and  four-component  mixture  can be
treated in the same way. The summaries are:
APPENDIX C                                                43

-------
Number of
components
in mixture
2
3
4
Number of
components
identified correctly
0
1
2
0
1
2
3
0
1
2
3
4
Probability of identifying
this number of components
by chance
30/56
24/56
2/56
60/336
180/336
90/336
6/336
24/1680
384/1680
864/1680
384/1680
24/1680
                           SCORING

    It is assumed that it is much better to get a score of j correct
than a score of j-1. Therefore, a quadratic scoring system is used. In
other words, there is no great trick in getting 1 out of 4 right, even if
chance is not involved, but a candidate who gets 4 out of  4 right is
doing very much better,  and we therefore credit him with being not
(4/1) times better but  (4/1)2 times better.  Therefore,  the score is
taken to be (the number of correct answers)2.

    The test program consists  of giving each candidate three  tests
(the test components are the same for each candidate).

                 Test 1:   two-component mixture
                 Test 2:   three-component mixture
                 Test 3:   four-component mixture

Candidates are selected on the following basis:

    Let the score of candidate 1 equal X and the score of candidate 2
equal Y.  Then the difference between scores is X — Y.

    When is this difference significant? What is the basis for choice
between candidates?

    The lowest possible total score isO-{-0 + 0 = 0.

    The highest possible total score is 22 -f- 32 -{- 4s = 29;  hence the
maximum difference (X — Y) =29 — 0 = 29.

    Table C4 lists all of the probabilities of difference between scores
from 0 to 29.
44                                                 APPENDIX C

-------
 TABLE C4 — DISTRIBUTION FUNCTION AND CUMULATIVE
  DISTRIBUTION FUNCTION FOR ABSOLUTE DIFFERENCE
IN SCORES OF ANY TWO SUBJECTS ON MULTICOMPONENT
             ODOR IDENTIFICATION TEST.
Difference
in score
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Probability of
Difference
0.1132
0.1518
0.1025
0.1397
0.1278
0.0938
0.0647
0.0511
0.0570
0.0370
0.0139
0.0148
0.0141
0.0062
0.0032
0.0037
0.0027
0.0011
0.0008
0.0006
0.0002
0.0001
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
Cumulative
Probability of
Difference
1.0000
0.8868
0.7350
0.6325
0.4928
0.3650
0.2712
0.2062
0.1554
0.0984
0.0614
0.0475
0.0327
0.0186
0.0124
0.0092
0.0055
0.0028
0.0017
0.0009
0.0003
0.0001
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
Nominal
Significance
Level






0.25
0.20
0.15
0.10

0.05



0.01



0.001

0.0001








APPENDIX C
45

-------
BIBLIOGRAPHIC: Turk, Amos. Selection and training of
   judges for sensory evaluation of the intensity and char-
   acter of diesel exhaust odors. PHS Publ. No. 999-AP-32.
   1967. 45 pp.

ABSTRACT: Exhaust gases emitted by diesel engines are
   characterized by offensive odors.  These odors must be
   rated  numerically by human judges with the ultimate
   objectives of  (1)  correlating such ratings  with the
   chemical composition of diesel exhaust  and (2)  estab-
   lishing Federal standards for control of diesel exhaust
   odors.  Judges are selected  on the basis of  (1) their
   ability to distinguish among odors of different intensi-
   ties and qualities, and  (2) their behavior in subjective
   testing  environments.   The  chosen judges  are then
   trained to improve their performance in odor discrim-
   ination, to become familiar with  diesel exhaust odor,
   and to rate the odor in terms of intensity and quality
   standards that  are provided to them  for reference.
   These standards comprise a scale of  overall odor  in-
   tensity, and four odor quality scales that correspond to
   the descriptions "burnt/smoky," "oily," "pungent/acid,"
   and "aldehydic/aromatic." Appendices describe (A) the
   theoretical basis  for air purification requirements in
   test chambers for odor studies, (B) the composition and
   makeup of the diesel odor standards, and (C) the math-
   ematical derivations of the statistical procedures.
ACCESSION NO.


KEY WORDS:

   diesel exhaust
   odors
   judging

   judges
   training
   standards

   mathematics
BIBLIOGRAPHIC: Turk, Amos. Selection and training of
   judges for sensory evaluation of the intensity and char-
   acter of diesel exhaust odors. PHS Publ. No. 999-AP-32.
   1967. 45 pp.

ABSTRACT: Exhaust gases emitted  by diesel engines  are
   characterized by offensive odors.  These odors must be
   rated numerically by human judges with the  ultimate
   objectives of  (1)  correlating  such ratings with  the
   chemical composition of diesel exhaust and (2) estab-
   lishing Federal standards for control of diesel exhaust
   odors.  Judges are selected on the basis of  (1) their
   ability to distinguish among odors of different intensi-
   ties and qualities, and  (2) their behavior in subjective
   testing  environments.   The  chosen judges are then
   trained to improve their performance in  odor  discrim-
   ination, to become familiar with diesel  exhaust odor,
   and to rate the odor in terms of  intensity  and quality
   standards that  are provided to  them  for reference.
   These standards comprise  a scale of overall odor  in-
   tensity, and four odor quality scales that  correspond to
   the descriptions "burnt/smoky," "oily," "pungent/acid,"
   and "aldehydic/aromatic." Appendices describe (A)  the
   theoretical basis  for air purification requirements in
   test chambers for odor studies, (B) the composition and
   makeup of the diesel odor standards, and (C) the math-
   ematical derivations of the  statistical procedures.
BIBLIOGRAPHIC: Turk, Amos.  Selection and training of
   judges for sensory evaluation of the intensity and char-
   acter of diesel exhaust odors. PHS Publ. No. 999-AP-32.
   1967. 45 pp.

ABSTRACT: Exhaust gases emitted by diesel engines are
   characterized by offensive odors. These odors must be
   rated numerically by human judges with the ultimate
   objectives of  (1) correlating  such ratings with  the
   chemical composition of diesel exhaust and  (2) estab-
   lishing Federal standards for control of diesel exhaust
   odors. Judges  are  selected on  the  basis of  (1) their
   ability to distinguish among odors of different intensi-
   ties  and  qualities, and (2) their behavior  in  subjective
   testing  environments.  The  chosen judges  are  then
   trained to improve  their performance in odor discrim-
   ination, to become  familiar with diesel exhaust odor,
   and  to rate the odor in terms of intensity and quality
   standards that are  provided to  them for  reference.
   These standards  comprise a scale of overall odor in-
   tensity, and four odor quality scales that correspond to
   the descriptions "burnt/smoky," "oily,"  "pungent/acid,"
   and  "aldehydic/aromatic."  Appendices describe (A) the
   theoretical basis for air  purification requirements in
   test chambers for odor studies, (B) the composition and
   makeup of the diesel odor standards, and (C) the math-
   ematical  derivations of the statistical procedures.
 ACCESSION NO.


 KEY WORDS:

    diesel exhaust

    odors
    judging
    judges
    training
    standards
    mathematics
 ACCESSION NO.


 KEY WORDS:

    diesel exhaust
    odors
    judging
    judges
    training
    standards
    mathematics

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