United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-450/4-83-01:
August 1983
Air
Analysis Of
Organic Compound
Data Gathered
During 1980 In
Northeast
Corridor Cities

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                          EPA-450/4-83-017

                                August 1983
    Analysis Of Organic
Compound Data Gathered
       During 1980 In
 Northeast Corridor Cities
               By
           Harold G. Richter
             Prepared For

    U.S ENVIRONMENTAL PROTECTION AGENCY
        Office Of Air, Noise And Radiation
     Office Of Air Quality Planning And Standards
    Research Triangle Park, North Carolina 2771 1

             August 1983

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            Analysis of Organic Compound Data Gathered During 1980



                         in Northeast Corridor Cities





Introduction



     During the  summer of  1980,  an extensive  air monitoring program  was



carried out  as  part of  the Northeast  Corridor Regional Modeling  Project



(NECRMP).  The primary purpose of the monitoring program  was  to  compile  an



air quality and  meteorological  data  base for use  in  photochemical  models.



Since most  of  these  models   require  ambient  concentrations  of  organic



compounds as part  of the  input  information,  one of  the  principal  efforts



of the  study  was to collect  samples of  air from major urban areas of  the



Corridor and  to  analyze  them  for  their  organic  species  composition.



     These data  can  be used  for purposes  other  than modeling.   They  can



be used to characterize  the area surrounding the point of collection,  for



example (i.e., the  emission  sources  in  the vicinity), or they can  be used



to estimate  the  contribution  of mobile  sources to the hydrocarbon burden



of the  air.   To  whatever  use  they  might  be  put, however,  the data  can



contribute to  reliable conclusions  only  insofar  as  the user  knows  the



qualifications and  peculiarities  of the data.    It  is the purpose  of this



report to acquaint  data  users with  the  large  body of ambient hydrocarbon



compositional data  acquired  during the  NECRMP,  to  alert  the  user   to



limitations in some  of the  data  from certain samples, and to show  how  the



data can be  used  for certain  analyses.   Complete data tapes  are available



as part of the  1980 Northeast Regional   Oxidant Study (NEROS) data compi-



lations from J.  H.   Novak,  Meteorology   and Assessment Division, Environ-



mental  Sciences Research Laboratory, U.S.  Environmental  Protection  Agency,



Research Triangle Park, North  Carolina 27711.

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Site Description and Analytical  Technique
     The Northeast  Corridor  extends  from  Washington,   DC,  in  the  south  to
Boston in the  north.   Samples  of air for  hydrocarbon  analyses were  collected
at surface  sites  in each  of four  metropolitan  areas  (Washington,  Baltimore,
New York  City-New  Jersey,  and  Boston),  as well   as  above  those areas  by  air-
craft.  Two  surface sampling sites  were chosen   in  each area, one  in a  high
traffic density, center-city  location, and  the other  in an  industrial  location.
Figures 1 thru  4  show  the  locations of  these  sites in each metropolitan  area.
     Two one-hour  integrated  samples of air  were collected  in Tedlar  and/or
Teflon bags  at each site  on most  days of the  monitoring program,  one  from
0600-0700 EOT  and  the  other from  0800-0900  EDT.  Aircraft  grab  samples  were
collected in  stainless  steel  canisters   at  various times and  locations  during
the day,  as prescribed  by  a protocol  determined by  the  meteorological  con-
ditions prevailing  on the  individual days.  Detailed  records  were made  of  the
flight paths and the locations,  altitudes and collection times of these samples.
When time permitted, a  third kind  of sample was   collected.  These were  called
"roving" samples  and were  grab  samples  collected  at  various  surface  sites
downwind of the Washington-Baltimore areas.
     Analysis of a sample was carried out as soon as  possible  after collection,
in order to avoid loss  of compounds  from the  containers.  The  elapsed  time  was
never more  than  24 hours.    Separate chromatographic and  data report  systems
were maintained for  each metropolitan area (although the Washington  and  Balti-
more systems  were  housed  in  the  same laboratory).   Battelle-Columbus  Labs
collected and  analyzed   samples  in  the  Boston  area,  while  We-jnington  State
University collected and analyzed samples from the other  three  areas.   Analysis

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Figure 1    Map showing sampling sites in the Washington,  DC area
                             -3-

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              BALTIMORE  AREA
Figure 2.   Map  showing sampling sites in the  Baltimore area,
                                 -4-

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Figure 3-  Map showing sampling sites  in  the  New York City area

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rigure 4.   Mao showing  sampling  sites  in  the  Boston  area

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was by  GC-FID  (gas chromatography  with  fl ame-ionization detection).   Details



of the columns and procedure have been presented elsewhere.1-5



     In all,  more than  1300  air  samples  were  collected  during  the  45-day



intensive data collection  period  from July 15  to August  30, 1980.   Only  1120



samples were analyzed, however, because of the  limited number of samples  which



could be analyzed  in  a  single day.  Table 1  summarizes  the number of  samples



analyzed from each site.



     Concurrent with  the  analysis  of ambient  samples,   an  extensive  quality



assurance/quality control   (QA/QC)  program  was carried  out.    This   included



regular analyses  of  a pentane or  neo-hexane  (2,  2-dimethyl  butane)  standard.



In addition,  each  of the  four  analytical  groups had  a  canister containing a



mixture of  14  organic   species   commonly  found  in  urban  atmospheres.    For



statistical purposes, each  group  analyzed the  mixture   at  least  eight  times



during the  July  15 - August  30  period.   Finally,  a  "round robin"  sampling/



analysis program  was  also included  in  the QA/QC program.   This consisted of



each analytical  group  collecting  an ambient  sample  in  a  stainless  steel



canister.  After analyzing a  fraction of the  sample, the  collecting group  then



sent the canister  to  one of  the  other  groups.   That group, in  turn,  analyzed



a portion  of  the  sample and  sent  the remainder  to a third group  which  repeated



the operation.   In all,  five  analytical  groups participated, and each  started



at least four  samples.   [The  fifth  group  was  from the Environmental   Sciences



and Research  Laboratory,  Research  Triangle  Park,  North  Carolina  (ESRL/RTP),



located in Columbus,  Ohio, at the time.]

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                                                            Table  1
                                              Summary Of Samples  From NECRMP  Sites
oo
                              Site

                   West End Library, Washington, DC

                   Takoma Park, Washington, DC*

                   University of Maryland

                   Read Street, Baltimore, MD

                   Essex, MD

                   Linden, NJ

                   Newark, NJ

                   East Boston, MA

                   Watertown, MA
                   Location

                   Washington - Baltimore

                   New York - New Jersey

                   Boston, MA
                   Location

                   Baltimore, MD - environs
                                                       Aircraft Samples
                                                        Roving Samples
Number of Samples^

       60

       16

       44

       82

       90

       81

       71

       85

       90
      619
Number of Samples

      286

       66

       86
      438
Number of Samples

       63
         Because uf space conflicts, the Takoma Park site in Washington,  DC,  had to be  vacated  early  in  the  study period.
         The university of Maryland site was then chosen to serve as  a  suburban  site for  the DC  area.

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Results and Discussion



     A.  QA/QC Program



         The results of the QA/QC program  are  reported  in detail  elsewhere.6»7



They are  summarized  here,  however,  because  they  are important to  the  discus-



sion of the  data  obtained  during MECRMP,  which  follows.   In brief, the  coef-



ficient of variation  for 20-25  analyses  of calibration  gas  (pentane  or  neo-



hexane) at each  laboratory  fell  between  five  percent and seven  percent.  This



is very  satisfactory.   Analyses  of the  standard  mixture  of 14  representative



organic compounds  showed  that the  individual  light compounds (carbon  numbers



of C-2 to  C-5)  could  be measured  with a  coefficient  of  variation of  15  per-



cent or  less,  but heavier   species,  particularly  aromatic   compounds,   were



subject to much greater errors.  Analysis  of data  from the round  robin  samples



shows that,  although  the various laboratories  generally  agreed  (+_ 15  percent



coefficient of  variation)  as to the  total  concentration  of compounds  present



(in parts  per  billion carbon, ppb  C), there  was  frequent disagreement  as  to



the identity of certain  of  the minor constituents, as well  as sometimes  large



disagreement (2-fold)   in  the concentration  of  total  identified  olefinic  and/



or total  aromatic compounds present.



         These results  show that light  organic species  can  be  measured  with



very satisfactory precision.  Heavier species are  measured with less precision.



The reasons  for  this  are  not  clear  at  the  present  time.    Some   evidence



(unpublished) has been  gathered  in  the past,  suggesting that passivated  stain-



less steel containers  may  affect the  behavior  of heavy  species,  particularly



aromatics, but  inconsistent  data  were obtained from the  aircraft  samples  and



the mixture of 14 species during  this study to corroborate the  point.

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         From one point of  view,  the round robin data are very  encouraging.
They show  that   skilled  analysts  can  measure   ambient  hydrocarbon  species
rather precisely  at the  ppb  C  level.   Different  analysts  usually  agreed
fairly well on  the  individual  concentrations  of most of the  lighter  species
(hexane and below)  which usually make  up about 50 percent of the total  concen-
tration.   When the data user needs to know only  the sum of hydrocarbon species
concentrations,  he  can  be confident  of  a fairly reliable value.  Much  work
needs to be done, however,  on  quantification  of the  heavier  species,  identi-
fication of  certain unknown  peaks,  and  the  frequent  irreproducibility  of
aromatic species data.   And, although  unrelated  to  the  present discussion,
all studies to date of  organic  compounds in ambient air have almost completely
neglected separation and  identification  of  the  oxygenated  and  substituted
species known or thought to  be present.   Whereas  these may be in low  concen-
tration,  a  complete characterization  of  the pollutant  burden  must  include
them.
         Nevertheless,  in  spite  of  the  above  restrictions,  because  of  the
excellent accuracy  and  precision  in  measuring  the  standard  sample and  the
hydrocarbon mixtures, these QA/QC  data from NECRMP should  allow data users to
have confidence   in  the  GC analytical technique  and  in  the  data obtained  by
experienced analysts.
     B.  Characteristics of the Data
         The chromatographic procedure used in analysis of NECRMP  samples is
capable of separating many compounds  in the individual samples.  Some of these
are identifiable on the basis of retention time.   That  is, they  appear on  the
chromatogram at   times  identical  to those  for  known  compounds.   Frequently,
                                      10

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other peaks appear  on  the  chromatogram at times different  from  those  times  at



which known compounds appear.  These peaks are called "unidentified compounds,"



and the  individual  concentrations are  summed  in order  to  estimate the  total



concentration of  all   organic  compounds  (excluding  methane)  in  the  sample



(sum-of-species, ppb C).



         During this  study,  60  or  more compounds  were  identified  in  the



samples.  These  are usually  divided  into  three major  chemical  groups  when



working with  the  data:   olefins,  paraffins  and aromatics.   One  of the  first



properties of hydrocarbon  data  sets  which many  analysts  look at is the  frac-



tional distribution of  total carbon  concentration  among the chemical  groups.



These distributions give  some  information as  to the major sources of  hydro-



carbons influencing the  receptor,  as well as pennitting a  rough  comparison  of



data obtained during studies in other cities.



         Table 2  summarizes  these distributions,  as well as  listing two  other



properties of the  samples  which warrant  discussion:  anomalous values  of  C2H4



(ethylene) and the  fraction  of  unknowns  in  the  samples.   First,  however,  the



reader may notice  that  the number of samples from each  site  listed  in  Table  2



may be  slightly  lower  than the  number  listed in  Table  1.   This is  due  to  the



fact that  duplicate samples  were collected  occasionally,  and their  analyses



are not included in the calculations of Table 2.



         The percentages of  the  species  were calculated  by  summing the concen-



trations of all members  of the  group (e.g.,  olefins)  and  dividing  by  the  sum



of all  identified  species  concentrations.  (The difference between  the  sum  of



these three percentages  and  100 percent  at  any given  site is the  percent  of



acetylene in  the  sample.)   From the  standard  deviations,  it is  seen  that the
                                      11

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                                                             Table 2
                                           Characteristics Of Data From Surface  Samples
	 1
Site
West End Library,
Washington, DC
Takoina Park,
'Washington, DC*
University of Maryland
Read Street, Baltimore
Essex, MD
Linden, NJ
Newark, NJ
East Boston, MA
Watertown, MA
Average - all sites
Number
of
Sampl es
58
16
43
80
89
71
71
85
90
603
	 1
[Average
Percent
Olefins* °
9.1 6.1
5.8 5.6
9.2 2.9
10.6 5.3
6.2 2.8
8.7 3.6
9.3 3.0
8.4 3.7
14.2 6.2
9.0 4.5
Average
Percent
Paraffins °
58.7 5.6
63.0 11.6
54.0 8.8
59.1 7.3
60.6 7.9
64.3 11.0
57.5 5.7
65.7 10.5
58.3 7.7
60.1 8.5
Average
Percent
Aromatics CT
28.8 7.0
28.0 9.5
33.8 9.7
27.5 7.7
30.9 8.4
25.4 12.3
30.3 6.9
23.2 7.4
24.3 5.7
28.0 8.3
Average
Percent
Unidentified
17.5
19.4
18.4
12.3
15.2
12.1
14.4
15.4
18.7
15.9
C2H4
Anomalies
# of Samples
36
12
2
27
51
42
15



*  Calculated from data for all  samples,  including those samples  for which  ethylene
   concentrations were recorded as zero.   See discussion on C2H4  anomalies.
                                                     -12-

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samples vary  appreciably  in  their  fractional   composition  of  some  of  the



groups, particularly the  olefins.   The paraffin  fraction,  on the other  hand,



is much  less  variable  (coefficient  of  variation)  among  samples  from a  given



site than are the olefins or aromatics.



         The penultimate  column of  Table  2,   called  "Average  Percentage  of



Unidentified," presents  a  characteristic   of   the  data  which  should  be  of



interest to data  users.   As  described  above,  unidentified compounds  are  those



which appear  on  the   chromatogram  at  retention   times  different  from  those



times at  which  known   compounds appear.  Little  or nothing  is known  about  the



chemical structure  of  these  compounds;  thus,  they  cannot  be placed  in  the



olefin, paraffin  or  aromatic categories.    If  the data user  is interested in



knowing the  total  concentration of  olefins  (or paraffins or  aromatics)  in a



sample, he  must  consider  the  probability  that  some  of  the  compounds  in  the



unidentified fraction  are  olefinic.   That  is,  the  total   concentration  of



olefins calculated  from   a  simple  summation  of the  identified olefins  in a



sample is  less  than  actually  existed  in   the  sample as  collected.   Without



more information  about  the  distribution  of  hydrocarbon  species  in ambient



air, it  would  seem that  the  only  alternative  a  data user  has  is to distri-



bute the unidentified  compounds among  the  three major groups  in the  same pro-



portion as  these  individual  identified groups  stand  to  the  total identified



hydrocarbon  concentrations  in  the  sample.   Put  more simply,  if the concen-



tration of  olefins  were  found  to  be  "X"  percent   of  the  concentration  of



identified compounds in  a given sample, then  the  data user  should assume, as



a first  approximation,  that  the  fractional  concentration  of  olefins  in  the



unidentified compounds  is  also  "X"  percent.   Whereas this will not change  the
                                      -13-

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fractional  relationships among the major groups, it  will  change  the  absolute
concentrations of the group sums,  as  well  as the calculated  group fraction  of
the recorded sum-of-species.  Table 3 shows  how these  concentrations  change,
using data from an actual  sample  (Read  Street,  Baltimore, 8/13/80, 0600-0700
EOT).
         Comparing columns 2 and 6, or columns 3 and  7,  shows  that there  is a
25 percent increase in the recorded concentration (or fraction)  of the group
sums if the  unidentified  compounds are  distributed proportionately among the
three groups.  Acetylene, of course,  remains the same concentration and frac-
tion, since  it  is  an identified species.   Such an increase in group  concen-
trations would very  probably  have  an  appreciable impact on  some  uses of the
data.
         The last  column  of Table 2,  "C2H4  Anomalies," requires  discussion,
too, since it may be of importance for some data uses.   After  analysis of the
samples, the  analysts  reported a  zero  value for  ethylene  concentration  in
each sample  for which there was evidence of ethylene  contamination.   Whenever
this contamination is  found,  it is almost  always in  samples  from monitoring
stations housing chemiluminescent ozone analyzers.   The reported  sum of  ole-
fins in samples  which were  contaminated  is, therefore, much  too small,  if
only the  concentrations  of  identified  olefins  are   summed,  since  previous
studies3'9 have shown that ethyl ene frequently makes up about half  of the total
olefin concentration  in  an uncontaminated  sample.   Table 2 shows that  many
samples seem to have been contaminated with ethylene  in  some of the stations.
         The problem with ethylene contamination affects other aspects of the
analysis of hydrocarbon data, although the  impact may be less  than it is  when
examining  only  the  olefin data.   The  total  sum-of-species  concentration,
                                     -14-

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 riroup
                                                            Table  3
                                            Summary Of  Data From  Surface Samples
                                         Read  St., Baltimore 0600-0700 EOT,  8/13/80

1
fin
tic
lene
if ied
it if ied

ppb C
in
Sample
53.5
306.5
145.5
12.5
518.5
123.8
641.8
Fraction
of
Total
0.083
0.478
0.227
0.019
0.807
0.193
1.000
Fraction of
Identified
(less acetylene)
0.106
0.606
0.288
-
-
-
-
ppb C
Unidentified
(fraction x 123.8)
13.1
75.0
35.7
-
-
-
-
Corrected
ppb C
66.6
381 .5
181.2
12.5
-
-
641 .8
Corre
Fract
0.1
0.5
0.2
0.0
-
-
1.0
 Olefin
 Paraf
 Aroma
 Acety
 IdiMit
i Un idei
 Tolxl

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as recorded, is less than it actually was in the  sample  by  the  amount  of the
missing ethylene concentration.   This will  typically cause an  underestimation
of the  sum-of-species   concentration by  about five  percent,   which  may  be
relatively unimportant for most uses of  the data,  but it may be  important for
some.  It  will  affect  the  calculated  paraffin   and  aromatic   fractions  (of
total hydrocarbon concentation)  to some  extent also.
         If the data user needs  to estimate the  value of a missing  ethylene
concentration, he has  two alternatives.   He  can  either assume the missing
concentration is equal  to that of the sum of all  other olefin  concentrations,
or he can calculate  the  average C2H4/C2H2 (ethylene/acetylene)  ratio in  uncon-
taminated samples from  the  same  sampling  site  and use  that  ratio and  the
acetylene concentration in the sample of  interest to  approximate  the missing
ethylene concentration.   Both methods  usually give similar  concentrations,
although the latter method is probably more correct.
         A different anomaly in ethylene concentrations is noted in data  from
samples collected and  analyzed  at  the  two  Boston  sites.   In  many of these
samples, ethylene  is  found  to  make  up 70-90 percent  of  the  total   olefin
compounds.  This cannot be attributed to a source  of ethylene  near  the  Boston
sites, however, as  shown  by  an  inspection of data  from  the round-robin  sam-
ples.  (Round-robin samples  were  grab  samples -- not  1-hour integrations  --
collected usually in  the  vicinity  of the  monitoring  stations and  were  thus
similar in species concentration to the  daily  samples.)  In  those  round-robin
samples collected in Boston, and analyzed by the  other laboratories, ethylene
made up about  50  percent  or less of the total olefin  concentration, similar
to that found  in  samples  from other areas.  Furthermore,  a  close analysis  of
                                     -16-

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the round-robin data shows that the Boston analysts reported ethylene concen-



trations very similar to those concentrations  found  by  other  analysts  of the



same samples.   It  thus  seems that  the  Boston  analysts  reported   fewer  or



smaller concentrations of  other  olefins in the samples, thereby  making  the



ethyl ene/total olefin ratios  high.   Whatever the  reason,  these  developments



introduce uncertainty as  to  the  reliability  of the  olefin  group  fractions



and, to  a  lesser extent,  of  other group  fractions  and sum-of-species  con-



centrations for the Boston sites.



     C.  Uses of the Data



         In addition to using  the NECRMP hydrocarbon species data for modeling



purposes, there are other uses which make the data  base  valuable,  in spite of



its limitations.  Some of these are discussed below.   Other uses  and analyses



will undoubtedly be made in the future.



         First, it is necessary  to  state,  explicitly, a rule which  all  data



users should  follow  when  using these data, as  well  as  when  using  all  other



data bases:   Simple  summaries of  data may be  very  misleading.   Data  users



should become very familiar with the details of the data base  they  work  with.



Whereas  it may be time consuming, it is imperative that users examine individ-



ual sample data, rather  than  summaries, in order to  avoid  arriving  at  wrong



conclusions.   The  rule   seems obvious,  but  it  is  too frequently  ignored.



         The value of this  rule should be clear from the  discussion above about



anomalies in  olefin  concentrations in  this data base.   Table 4 shows  how a



simple summary of average olefin fraction (all samples)  at  the various  NECRMP



sites differs from a summary of average olefin fraction  of  only  those samples



in which ethylene concentrations were reported.   Large  errors in calculated
                                     -17-

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                                                             Table 4


                                                  Comparison of Olefin Fractions

                                          All Samples Vs. Only Those Reporting Ethylene
Site
West End Library,
Washington, DC
Read Street, Baltimore, MD
Essex, MD
Linden, NJ
Newark, NJ
East Boston, MA
Water town, MA
mean
0.091
0.106
0.062
0.087
0.093
0.084
0.142
Al 1 Sampl es
a
0.061
0.053
0.028
0.036
0.030
0.037
0.062
n
58
80
89
71
71
85
90
mean
0.139
0.122
0.077
0.100
0.097
0.084
0.142
Only Those With C2H4
a
0.048
0.053
0.033
0.035
0.026
0.037
0.062
n
22
53
38
29
56
85
90
CD
I

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olefin fractions  are  thus  possible  at  some  of  the  sites  if the  ethylene
problem is unknown or ignored.  Olefin  fractions  at the two  Boston  sites  are
included in Table 4 for comparison with the other sites.   It  is apparent  that
a significant difference in the spectrum of hydrocarbon species  exists among
the several sites, although more data are necessary in order  to determine  how
statistically important this is.
         1.  Compound/Acetylene Ratios
             One use to which hydrocarbon species data is  sometimes  put is  to
estimate the contribution  of automotive emissions  in the samples.  This  is
done by assuming -  and  it  is usually  a  sound assumption - that the only source
of acetylene is  from automobiles.  If  one  knows  the fraction  of  acetylene  in
auto exhaust,  then the  olefin/acetylene  ratio  or the  paraffin/  acetylene
ratio in  an  ambient sample  is  a measure  of  automobile contribution to  the
hydrocarbons in the sample.  These fractions have  been measured  in  both pure
exhaust^ and in  highway tunnels.3,9,11  Table 5  summarizes these  NMHC/acety-
lene ratios.
             There is  some  agreement  among ratios, but the  contribution  of
auto exhaust  to observed  hydrocarbon  levels  in  ambient  samples  cannot  be
asserted too rigidly.  Using Lonneman's  ratio from the  recent Lincoln Tunnel
study for  total  NMHC/acetyl ene  of  29.7,  which  is believed  to  be the most
representative of  exhaust  from  the  current mobile source fleet,  the percent
of automobile  contribution  to  observed  hydrocarbon  concentrations  at  the
various NECRMP  sites  can  be  estimated by multiplying the average  acetylene
concentration by 29.7  (giving  an estimate  of  the HC  sum-of-species concen-
tration contributed  by mobile  sources)  and  dividing  that   product  by  the
average HC  sum-of-species   concentration at  the  site.  Table 6  shows  these
                                     -19-

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                                                             Table 5
                                   Nonmethane Hydrocarbon/Acetylene Ratios in Auto Exhuast
1
Ratio
01 ef in/Acetylene
Paraffin/Acetylene
Aromatic/Acetyl ene
Total NMHC/Acetylene
Black8
(exhaust)
4.7
10.2
3.0
22.0
Lonneman^
(tunnels)
3.24
6.81
3.87
13.90
Lonneman^
(Houston)
3.08
7.59
5.22
15.90
Lonnemanll
(Lincoln Tunnel )
6.05
13.1
9.53
29.7
I
ro
CD
i

-------
                                                          Table 6
                              Estimated Automobile Contribution To Observed HC Sum-of-Species
IXi



I
Site
West End Library,
Washington, DC
University of Maryland
Read Street, Baltimore
Essex, MD
Linden, NJ
Newark, NJ
East Boston, MA
Watertown, MA
Acetylene
ppb C , average
17.8
16.5
15.6
11.1
10.6
12.6
12.1
7.7
HC Sum-of-Species
(ppb C, average)
714
666
639
606
961
510
777
352
Percent
Auto
74
74
72
54
33
73
46
60

-------
results.
             At four of the  sites,  one  may conclude that more  than  70 percent
of the observed hydrocarbons come  from  auto exhaust.  The Linden, New Jersey,
site shows a  smaller  contribution  from  automobiles.   However,  there  is a large
refinery nearby, and a more detailed analysis of the data would  be  required to
establish the impact from this  source more firmly.   Similarly,  a petroleum tank
farm was located upwind (on certain days) from the East Boston  site.   On these
days, the total hydrocarbon concentration in the samples was several  ppm C, most
of it paraffinic.   Excluding these  data  from the  calculation   would  increase
the estimated  mobile  source contribution  to nearer 70  percent.  This  higher
number for automobile contributions  to  ambient hydrocarbons  would then  reflect
the situation  which  prevails  around  the  sampling  site  most  of  the  time.
             There is no rigorous  proof  of  the  correctness  of this  method for
estimating the  fraction of mobile  source contribution  to  ambient hydrocarbons.
The basis seems sound, and the  calculated fraction  agrees  with  one's  impression
of mobile sources  in  the  neighborhood,  but  an experimental  program  to test the
the assumptions would be very difficult  to mount.
             Another example of compound/acetylene  ratio  analysis can show  how
this technique  may  help  characterize the vicinity around a  sampling  site,  as
well as to illustrate  how  the  use  of data summaries without a  critical  review
may be mi sleadi ng.
             Some hydrocarbon compounds  in  the  ambient  air  usually  come from
a limited number  of  sources.   Large concentrations of  ethane, for  example,
probably have  commercial  natural   gas  as their  source.   Large  concentrations
of propane probably  come  from  liquefied petroleum  gas  sources.  Benzene and
toluene generally come  from  evaporated  solvents,  while n-butane and i-pentane
                                       22

-------
come from gasoline  vapors.   Since the absolute concentrations of  any  of these



species may  vary  from  site  to  site  (because  they  also  are  found  in  auto



exhaust), the  best  way to  compare  one site  with  another is by  comparing  the



compound/acetylene ratios (i.e., acetylene is a normalizing factor).



             The average n-butane/acetylene and i-pentane/acetylene ratios



in atmospheres not  dominated  by point sources of  these two  compounds  is about



3 and 5,  respectively.13  These ratios are  found  at all  of the  NECRMP  sites,



except East  Boston  and Linden,  where they  were  12.5 and  15.7,  respectively.



This indicated a  probable  source of gasoline evaporative loss in  the  vicinity



of the  site.   Closer  examination  of the  individual  sample data  for  the  East



Boston site,  however,  showed  that  in  only  a  few  samples  were  these  ratios



elevated.  All  others were  in  the  customary  range.  On  those   certain  days,



the ratios  were  very  high  (100-300).   These dominated the  averaging  process,



potentially leading  to an  erroneous  conclusion  that the  site was continually



surrounded by such a source.



             Examination of wind directions on those days  of high ratios  showed



that the wind was always from the NW, 310°-350°.   The sum-of-species concentra-



tions on these  days  always exceeded  1  ppm C.  The  conclusion  seems  now  very



clear:  there  was a  large  source of butanes  and  pentanes,  probably from  evapo-



rative emissions, NW of the  East Boston  site.   On further investigation,  it



was found that  a gasoline  storage  tank  farm was  located  at some  distance  NW



of the site.   In  retrospect,  the choice of the  location  for the  monitor  proved



to be a  less than  ideal location  at which  to measure  hydrocarbons.   However,



this was suspected when the siting decisions were being made, but other factors



dictated locating the  hydrocarbon monitor at this site.
                                     -23-

-------
         2.   Sum-of-Species/NMOC Comparisons
             Another use to  which  species  data  are  put is  to  compare  sum-of-
species concentrations  with  concentrations  of total NMOC recorded  by collocated
continuous instruments.   At  seven  of  the  sampling  sites  (Read St.,  Baltimore;
Essex, MD;  West  End  Library,  DC;  Linden,  NJ;  Newark, NJ;  East  Boston;  and
Watertown, MA),  continuous  NMOC  analyzers  (MSA  11-2)   were  set  up  to  measure
ambient hydrocarbons  during  the NECRMP-  These  insruments  were calibrated  with
great care  (propane  standard)   and maintained   by  experienced  technicians  in
order to  gather  the  best data possible.  They  sampled  ambient  air  from  the
same manifold  which supplied  air to the Teflon/Tedlar bags  for  species  analysis.
Analysis of data  from these  simultaneous  hourly measurements may  be  interpreted
in more than  one  way:   a  comparison of how well  (or poorly) behaved  are  contin-
uous NMOC  analyzers  compared  with  the  sum-of-species;  how  comparable  are  the
data from  different instruments of  the  same  make;  or  how confident  a  modeler
might be in using NMOC instrument data  for ozone modeling.
             Figures 5  thru  11  show the  results  of  comparisons  of NMOC  data
from analyzers  with  sum-of-species.  Data  have been plotted  on log-log  scales
in order  to  simplify comparison of  the  different  sites.    Such  plots  provide
greater resolution  at the lower end of the scale than  do linear plots,  as  well
as allowing percentage  differences  to  be read directly  from  the  plot.   Sum-of
species includes  the  unidentified compounds,  as well  as the  identified species.
As noted  previously,  no  correction  was  made to  the   sum-of-species  data  for
missing ethylene  concentrations in  those samples  where ethylene  contamination
was evident (and  the  ethyl ene  concentration   was  recorded  as zero).   To do  so
would increase  all   sum-of-species   concentrations   by   a  few  percent,  thereby
translating some of the  points in the figures  slightly to the right.
                                     -24-

-------
    5.0


    4.0



    3.0




    2.0
O   1-0

£
o.
a

cc
in

£   0.5
_l

I   0.4

<

O   0.3
O



1   0.2
    0.1
   0.05
                 0.1
0.2   0.3  0.4 0.5       1.0


       SUM-OF-SPECIES, ppm C
2.0   3.0  4.0  5.0
         Figure 5.   Hest End Library:  NMOC Analyzer   Sum-of-Soecies Conpariscn

-------
    5.0


    4.0


    3.0 —




    2.0
    1.0
0.
Q.

OC
LU

£   0.5


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   0.05
                 0.1
0.2   0.3  0.4 0.5        1.0


       SUM-OF-SPECIES. ppmC
2.0   3.0  4.0  5.0
         Figure  6.   Read Street,  Baltimore: NMOC  Analyzer  -  Sum-of-Species  Comparison
                                            -i.0-

-------
    5.0
    4.0
    3.0
    2.0
a   1.0
EC
UJ
N
2   0.5
O   0.4
O
2   0.3
    0.2
    0.1
   0.05
                0.1
0.2   0.3  0.4  0.5        1.0
       SUM-OF-SPECIES, ppm C
2.0   3.0  4.0  5.0
          Figure 7.  Essex,  MD:  NMOC Analyzer  -  Sum-of-Species  Comparison

-------
      0.1        0.2    0.3  0.4 0.5       1.0        2.0    3.0  4.0 5.0
                         NMOC ANALYZER, ppm C

Figure 8.  Linden, NJ:  NMOC  Analyzer - Sum-of-Species  Comparison
                                -28-

-------
    5.0


    4.0


    3.0




    2.0
o   1.0

Q.
o.
cc
01
N
>
_J


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0
o


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0.2
    0.1
   0.05
                           l!_3L
                0.1
                      0.2   0.3  0.4 0.5       1.0


                             SUM-OF-SPECIES, ppm C
2.0   3.0 4.0 5.0
          Figure  9.   Newark, NO:  N'MOC Analyzer - Sum-of-Species Comparison
                                       -29-

-------
   5.0


   4.0



   3.0





   2.0
O
i—


I


ec
in
M
2   0.5


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    0.2
   0.1 —
  0.05
              1:1
                0.1
0.2   0.3  0.40.5        1.0


       SUM-OF-SPECIES, ppm C
2.0   3.0  4.0 5.0
        Figure  10.   East Boston, MA:  NMOC Analyzer  -  Sum-of-Species  Comparison
                                        -3Q-

-------
0.05
              0.1
0.2   0.3  0.4  0.5       1.0
        SUM-OF-SPECIES, ppm C
2.0   3.0 4.0 5.0
     Figure II.  Watertown,  MA:  MMOC Analyzer - Sum-of-Species  Comparison

-------
             Perfect agreement between all  of  the measurements would  have  all
of the data lying on the 1:1 line.   There is no absolute way to determine which
of the measurements in such a comparison is correct.  There  is  some  justifica-
tion, too, for thinking that the two procedures do not measure equally  well  the
same species in  all  the  samples.   Because of the  known difficulties with  con-
tinuous NMOC instruments,10.12 however, and the satisfactory  results  which  the
five analytical groups obtained in  analyzing the round-robin samples  (_+ 15  per-
cent coefficient of variation in sum-of-species, 65 analyses), it  seems reason-
able to assume,  for  this  study,  that the sum-of-species procedure yields more
uniformly reliable data than do the NMOC  instrument readings.
             Little can  be  generalized  about  these comparisons.   It  must  be
borne in  mind  that the NMOC  instruments  were   not  maintained as  well  as  they
would have been  in  a well   controlled  laboratory  study.   Thus, there  could  be
some slight  inaccuracies in  sample  timings  (both  NMOC data  and  species collec-
tion timing), calibration,  voltage  and/or temperature  fluctuations,  or perhaps
other problems.   Nevertheless,   the  data   obtained  from  the  instruments   is
thought to be  the  result of  above average  attention to technical details  and
to be an accurate representation of the data obtainable from these instruments.
             At most of  the  sites,  the data scatter widely.  Only at  the  East
Boston site  (Figure  10) does  there  seem to  be  consistent  agreement  between
the two methods, although there  is a positive  bias of  about  15 percent in  the
NMOC continuous  instrument  data.   Table  7  summarizes  statistical  information
about the  least  squares analysis  of these  natural  logarithmic data.    As  the
table shows,  only data from the East Boston  site exhibit a  high r-square value.
             At five of  the  sites,  half  or  more  of  the  samples contained  less
than 600 ppb C of hydrocarbons.   This is  of  some concern,  since the comparisons
                                     -32-

-------
                                                         Table  7
                               Sum-of-Species/NMOC Comparisons,  Least  Squares  Regressions
OJ
(.0
Site
West End Library,
Washington, DC
Read Street,
Baltimore, MD
Essex, MD
Linden, NJ
Newark, NJ
East Boston, MA
Watertown, MA
Slope
0.552
0.113
0.835
0.531
0.987
1.108
0.750
Intercept
- 0.552
- 0.283
- 0.101

- 0.277
+ 0.095
- 0.568
Standard Error
0.672
0.713
0.599
0.865
0.574
0.327
0.574
r-square
0.169
0.0077
0.354
0.141
0.467
0.887
0.475

-------
of NMOC data  and  sum-of-species  show  that there  can  be large differences  in



concentrations, as measured by  the  two  techniques.  Data from the NMOC  analy-



zers were  all   carefully  examined  by  the  contractor   responsible  for  their



operation.  All questionable  data were discarded;  thus,  only "verified"  NMOC



data - that which might be  used by an agency for  its  regulatory  purposes have



been archived.   There  is  good  reason to  expect  no  more  accurate  data  from



NMOC instruments  in  routine field monitoring programs  which  are  likely  to  be



maintained with less care than  were the instruments in  this  study.   The  poten-



tial for  large  error in  hydrocarbon  concentration data  is  then  reflected  in



greater uncertainty  in modeling   predictions,  if  the   continuous   instrument



data were to be used for this purpose.



             The NMOC instruments  should   not have been  affected by  ethylene



contamination, as  were  the  samples destined  for  species  analysis,  for  the



following reason.   Most,  if not  all,  of   the collocated  ozone analyzers  were



fitted with  ethylene oxidizers  which  were  designed   to  destroy  the  excess



ethylene after it left the ozone instrument.   Thus, assuming  properly  func-



tioning oxidizers, no ethylene  should  have been  exhausted to outside  where  it



could be entrained in manifold  air from  which all instruments (including both



the Tedlar  bags  and the  NMOC  device)  sampled.   Moreover,   if  ethylene  had



entered the NMOC instruments  through entrainment,  concentrations  of NMOC from



these monitors should have  been surprisingly  large, most if not  all the time,



since the ozone and  NMOC  instruments  were  running continuously.   On the  other



hand, leakage  of  ethylene  at  the  instrument and from  plumbing connections



inside the monitoring shelters  could have  exposed the  Tedlar bags to  about  24



hours of  a  low level  (ppm)  ethylene  atmosphere.  Small  molecules,  ethylene



particularly, are known to  diffuse readily through thin Tedlar membranes.   No
                                        34

-------
such diffusion is possible into the  NMOC  instrument.  This is  not  a  completely
satisfying explanation, because it  is  difficult  to believe,  with  the  air  con-
ditioning maintained in the sampling stations,  that much ethylene could collect
and diffuse into the  bags.   In summary, the source of  the ethylene  contamina-
tion of GC samples at certain times is unknown.
             In a laboratory  studylO comparing  continuous  NMOC analyzer  data
with sum-of-species  data,  smaller  scatters  of  data  were observed.    In  that
referenced study, more than 80  percent of  the  NMOC data  from the  MSA  11-2
instrument lay above  the  1:1  line.   The  slope  was  1.06 and  intercept 0.079,
n = 48,  and  r^ = 0.951.  These studies show that  much  more  work  is needed  to
resolve the differences or  to  get  better,  consistent agreement between these
two measurement techniques.
         3.  Sum-of-Species/NOx Ratios
             At some  of the sites,  NOX chemiluminescent  analyzers  were  used
to measure ambient  NOX concentrations.   Not as  many  data  were  collected  from
these instruments as  was  desired because  of malfunctions.   Table  8  shows the
average sum-of-species/NOx  ratios.   The  hourly  sum-of-species  averages  have
been listed for  all  sites  studied,  as well as  the (simultaneous) hourly  NOX
averages.  (Note that  the  sum-of-species/NOx ratio recorded  for the  sites  in
Table8  is not  obtained  by  dividing  the  average sum-of-species  by   average
NOX.  The  ratios  in column  3   were  obtained by averaging all  the individual
sum-of-species/NOx ratios  recorded at those sites.)
             Except as  described  below,  all  data  pairs  were  used  for these
averages, including those hydrocarbon  samples  which exhibited  C2H4 anomalies.
Correction of these samples  for missing C2'ri4 concentrations  would  increase the
ratios of Table 8 by less  than  five percent.
                                     -35-

-------
                                                            Table 8
                                                    Sum-of-Species/NOx Ratios
Site
West End Library,
Washington, DC
University of Maryland
Read Street, Baltimore
Essex, MD
Linden, NJ
Newark , NJ
East Boston, MA
Watertown, MA
Sum-of -Species
(Average)
0.714
0.666
0.639
0.606
0.961
0.510
0.777
0.352
NOX
(Average)
0.094

0.095
0.074
0.059

0.063

Ratio (Average)
+ Standard Deviation
13.5 + 10.7

9.1 + 5.4
10.7 + 5.4
23.9 + 28.5 (16.2 + 9.9)*
( n ^ 61 )

31.3 + 79.7 ( 9.6 + 6.3)*
( n ^ 61 )

n
56
--
49
28
65
--
78

OJ
en
             * Certain high ratios eliminated for these calculations (see text).

-------
             The high  ratios  in  Linden,  NJ  and East  Boston,   MA  stand  out,



including the high  standard  deviations  for data  from  these two sites.   Since



there is a  petroleum  refinery  near the Linden site and a tank  farm  upwind (on



certain days) of the East  Boston  site,  the  individual  sample  data  were inspec-



ted to determine if more information could  be  gleaned  from  an analysis of less



source-specific data.



             Data from  the  Linden site show  that two  of  the  individual  sum-



of-species/NOx ratios were above  134,  and  two others were  above 80.   In  three



of these four,  the  NOX  concentrations  seemed very low  (around  0.01-0.02  ppm),



while the  fourth  had a  sum-of-species  concentration of more than  6.8 ppm  C.



Eliminating these questionable  samples  from the  calculations reduces  the  sum-



of-species/NOxratio for  the  Linden site to 16.2 +_  9.9  (n  = 61),  which  is  a



ratio comparable to  the  other cities.   On  the other hand,  it  should  be  borne



in mind that relatively  large sum-of-species  /NOX ratios may  be characteristic



of highly industrialized areas.



             Similarly, eliminating from the  calculations  those  samples   col-



lected at the East Boston site during which the  wind was from the direction  of



the tank farm  gives a  sum-of-species/NOx  ratio  of 9.6 _+ 6.3 (n = 61).   This



ratio is now in line with the other three  sites in Table 8.



             All data pairs were  used  for  the calculations  of Table 8, except



those noted in the above two paragraphs. A more  informative number is  the  sum-



of-species/NOx ratio on  those days which  experienced  high  ozone values  later



in the day   at a  downwind monitoring site (although it is recognized that  other



factors - mainly meteorological  -  also  contribute to the formation of  ozone).



Using only  these days of high ozone for the HC/NOX ratio calculation  eliminates



periods when other  factors (1 ow temperature,  cloud cover, adverse  winds,  etc.)

-------
mitigate against ozone formation.   Table  9  summarizes these data for  all  days
on which an  ozone concentration  of 0.15 ppm,  or greater,  was  recorded at  a
site within  about  50 miles  of  the station  where  hydrocarbon  and NOX  concen-
trations were  measured.   Table  9  also  shows NMOC/NOX  ratios  on  high  ozone
days together with sum-of-species/NOx and NMOC/NOX ratios (from Table  8)  on  all
days of  observation.   These NMOC/NOX  ratios were  included in  order to  gain
some impression of the  differences a photochemical modeler  (particularly  with
the EKMA)  might  find if he  had  only continuous  NMOC  instrument data to  use.
             The comparison of ratios on  high  ozone days does not seem  as  bad
as does the  comparison of ratios  on all days.  But, as stated  earlier,  statis-
tical summaries  should  be  used  with great  caution.  If  the individual  data
which make  up  these   summaries  are examined, the  photochemical  modeler  would
have reason  to be concerned.   Table 10  shows  the  sum-of-species,  NMOC,  and
NOX data on  high  ozone days during  the  NECRMP  in Essex, MD together  with  the
calculated ratios.   A similar picture  of the data  is  seen at  all  the  other
sites on  high  ozone  days:   there  is  frequently  a  great  difference  between
sum-of-species/MOx ratios and  NMOC/MOX  ratios on  days   of  interest to  photo-
chemical modelers.   Clearly, more work  is needed to reconcile the  differences
in data obtained from these two measurement  techniques.
             More can be gleaned  from Table  9.   Both the Essex  and  the Linden
sites show sum-of-species/NOx ratios quite different from the other  three sites
on high ozone days.  These two sites would probably be classified as  industrial
sites on the basis of these data, both  exhibiting an excess of  hydrocarbon  as
compared with sites influenced mostly by automobile exhaust.  This is  borne  out
to some  extent  by the data  in  Table 6.  There,  it  is  estimated that  only  54
percent of the measured  hydrocarbons  come from  automobiles at the Essex site,
                                     -38-

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                                                         Table 9
                                         Hydrocarbon/N0x Ratios On High Ozone Days


Site
West End Library,
Washington, DC
Read Street,
Baltimore, MD
Essex, MD
Linden, NJ
East Boston, MA
Ratio - Higf
Sum-of-Species/NOx
mean a n
7.8 3.6 16
6.9 2.7 15
12.8 8.9 10
13.5 5.6 33
6.0 0.5 4
i 03 Days
NMOC/NOX
mean o n
6.6 2.8 16
10.8 5.3 15
12.0 7.3 10
11.6 10.5 29
7.4 0.9 4
Ratio -
Sum-of-Speci es/NOx
mean a n
13.5 10.7 56
9.1 5.4 49
10.7 5.4 28
23.9 28.5 65
31.3 79.7 78
All Days
NMOC/NOX
mean 0 n
6.2 3.2 51
12.9 12.6 36
11.1 5.7 27
14.2 20.2 60
19.6 29.1 73
I
CO

-------
                           Table 10
Sum-of-$pecies/NOx And NMOC/NOX On  High  Ozone  Days  In  Essex, MD
Date

8/14

8/24

8/26

8/27

8/29

	 1
Samp! i ng
Time

6-7
8-9
6-7
8-9
6-7
8-9
6-7
8-9
6-7
8-9
Sum-of-Species
ppmC

0.676
0.593
0.339
0.236
0.944
0.793
2.755
0.984
0.516
0.552
NMOC
ppmC

0.90
0.78
0.27
0.18
1.14
1.17
2.22
0.60
0.45
0.48
NOX
ppmC

0.099
0.120
0.050
0.013
0.081
0.106
0.159
0.137
0.039
0.016
Sum-of-Speci es/NOx
Ratio

6.8
4.9
6.8
18.2
11.6
7.5
17.3
7.2
13.2
34.5
NMOC/NOX
Ratio

9.1
6.5
5.4
13.8
14.1
11.0
14.0
4.4
11.5
30.0
Ozone
ppm

0.15

0.15

0.17

0.18

0.15


-------
and only  33  percent at  the  Linden  site.   In  contrast, hydrocarbons  at  the



West End Library site were estimated as 74 percent automotive;  the University



of Maryland  site  also  as 74 percent;  Read  St,  Baltimore as 72  percent;  and



Newark, NJ as 73  percent.  The two  Boston  sites  were lower,  particularly  the



East Boston site,  where the estimation was probably heavily  influenced by  the



few days  when  wind  was   from  the  direction of  a  source  to the  northwest.



         4.  Aircraft and Roving Van Sample Data



             Only a  few  words  need be  said  about samples collected  by air-



craft and  roving  vans.   The  data user  would be  well advised to  examine  the



individual sample data,  rather  than summaries  of  the  data.   Because  of  the



frequently very low  concentrations  of  species  in the samples (80  percent  of



the aircraft samples and  20  percent of the roving van  samples  had less than



100 ppb C total hydrocarbon), there  is  great opportunity  for large errors  in



the group  fractions.   The unidentified components of  some   aircraft  samples



exceed 50 percent of the total.   Some aircraft samples are  reported  to have



no olefins,  others  no  aromatics.   In  some  samples,  the sum of aromatics  is



reported to exceed the  sum of paraffins.



             The roving van data,  too,  must be  examined  carefully.   It  may  be



that the  chromatograph was  not  functioning properly during   analysis of some



of the  samples,  because   some of  the most  commonly  occurring  aromatics are



reported missing.    In  other  samples, ethylene is  the  only   reported  olefin.



These results are  very unusual, and the  user  must assure himself, by using



other information or by   consulting  chemists,  that the  reported  numbers are



reliable.
                                       41

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Summary

     1.  During the 1980 Northeast Corridor  Regional  Modeling Project (NECRMP)
about 1120 ambient air  samples  were  collected and analyzed from  surface  sites
and by aircraft  for  hydrocarbon species analysis.  The  surface sites  were  in
the metropolitan areas  of  Washington,  DC,  Baltimore,  New York-New Jersey,  and
Boston.
     2.  An extensive QA/QC program  carried  out during the NECRMP showed  that
five participating laboratories  could analyze standard gases  repetitively  with
a coefficient of variation of 5-7 percent.  C-2 to C-5 compounds  in  a standard
mixture of 14 compounds were measured repetitively with a coefficient of  vari-
ation of 15 percent.   Heavy hydrocarbons,  particularly  aromatic species,  were
measured with much less precision.   Round-robin  samples  (ambient samples  col-
lected and analyzed by one participating laboratory,  then sent  for consecutive
analyses by all  other  participants)  showed reasonable agreement (+_  15  percent
coefficient of  variation)  as  to  total  concentration of hydrocarbons in  the
samples, but there was frequent disagreement  as to identification and quantity
of some of the minor species.
     3.  There was an average of 16  percent (in concentration)  of unidentified
species in the  619  surface samples  analyzed.   Aircraft  samples averaged  much
more.  About 45  percent of the  surface  samples  analyzed at  six  of  the  eight
sites evidenced  anomalous  ethylene  concentrations or ethylene contamination.
     4.  Data users  are advised to  examine  data  from the individual  samples,
rather than rely on summary statistics  of those  data,  because  of the  character-
istics summarized in "3" above.
                                     -42-

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     5.  Mobile  source  contribution to the  observed  hydrocarbon  at  each  site



was estimated.   Automobiles  were  calculated to contribute  more  than 70  per-



cent of the  hydrocarbons  at  four of the  eight  sites, but the method  of  esti-



mation is difficult to  verify,  thus the  reliability  of the estimate  may  have



1imited useful ness.



     6.  A comparison of sum-of-species concentration  with data from collocated



NMOC continuous analyzers  was made.   There  was reasonable agreement  among  the



data points  at only one  of the  seven  sites  having NMOC  instruments.   Assuming



sum-of-species data are more uniformly  reliable than  data from the  continuous



instruments, these latter  did not agree very  well  with GC  measurements  under



field conditions  on this  project.   Even at sum-of-species concentrations exceed-



ing 0.5 ppm  C, there  was  reasonably good agreement between  the two methods  at



only three of the sites.



     7.  Sum-of-species/NOx ratios  were  computed for  sites  where  NOX instru-



ments were  collocated with  species samplers.   Computations  were  made,   both



for all days  and  for those  days  when  ozone concentrations  greater  than  0.15



ppm were  recorded downwind of  the metropolitan  areas.  The  average of  this



latter ratio  differs  by  more   than  2-fold  between   certain  cities,  but  the



number of high-ozone  days  was relatively  few,  and thus  the  statistical signi-



ficance of the data is open to  question.



     8.  Sum-of-species/NOx ratios were compared  with  NMOC/NOX ratios, both  on



high-ozone days and on all days   for which data  were available.  The average  of



the ratios by  these two  methods on high  ozone  days  seem to agree  better  than



the average of the ratios on all days  for which data are available,  but compar-



ison of individual day's ratios  show large differences.



     9.  The  fractions  of species  groups  (olefins,  paraffins, and  aromatics)




were shown to be  fairly  uniform  among  the  four  metropolitan areas.





                                     -43-

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References

1.   W. A. Lonneman,  "Ozone and Hydrocarbon  Related Measurements in Recent Oxidant
     Transport Studies,"  International  Conference on Photochemical  Oxidant Pollution
     and Its Control,  Proceedings:  Volume  I,  EPA-6QU/3-77-001a, U.S. Environmental
     Protection Agency,  Research Triangle  Park, NC 27711, January 1977, pages 211-223.

2.   H. H. Westberg,  R.  A.  Rastnussen, and  M.  Holdren, "Gas C'nromatographic Analysis of
     Ambient Air for  Light  Hydrocarbons  Using a Chemically Bonded Stationary Phase,"
     Anal . Chem. 46_ (1974).

3.   W. A. Lonneman,  S.  L.  Kopczynski,  P.  E.  Darley, and F. D. Sutterfield, "Hydro-
     carbon Composition  of  Urban Air Pollution," Env. Sci. Tech. 8(3) 229 (1974).

4.   H. Westberg,  K.  Allwine,  and E. Robinson, "Measurement of Light Hydrocarbons and
     Oxidant Transport,  Houston Area, 1976,"  EPA-600/3-78-062, July 1978.

5.   R. L. Seila,  "Nonurban  Hydrocarbon  Concentrations in Ambient Air North of Houston,
     Texas," EPA-600/3-79-010,  February  1979.

6.   H. H. Westberg,  W.  A.  Lonneman, and M.  Holdren, "Analysis of Individual Hydro-
     carbon Species in Ambient Atmospheres - Techniques and Data Validity," American
     Chemical  Society  Annual Meeting, Kansas City, MO, September 1982.

7.   W. A. Lonneman —  to  be  published.

8.   F. Black  and L.  High,  "Automotive  Hydrocarbon Emission Patterns and the Measure-
     ment  of Nonmethane  Hydrocarbon Emission Rates," Paper 77-0144, International
     Automotive Engineering  Congress and Exposition, Detroit, February 28 - March 4,
     1977.

9.   W. A. Lonneman,  G.  R.  Namie, and J. J.  Bufalini, "Hydrocarbons in Houston Air,"
     EPA-600/3-79-018, February 1979.

10.  F. W. Sexton,  R.  M.  Michie,  Jr., F. F.  McElroy, and V. L. Thompson, "A Compara-
     tive  Evaluation  of  Seven  Automated  Ambient Nonmethane Organic Compound Analyzers,"
     EPA-600/54-82-046,  August 1982, Environmental Monitoring Systems Laboratory,
     Research  Research Triangle Park, NC 27711.

11.  W. A. Lonneman,  Lincoln Tunnel Studies,  1982 --- unpublished data.

12.  L. R. Rechner, "Survey of Users of  the  EPA Reference Method for Measurement of
     Nonmethane Hydrocarbons in Ambient Air," EPA-650/4-75-008, December 1974;
     F. F. McElroy and V. L. Thompson,  "Hydrocarbon Measurement Discrepancies Among
     Various Analyzers Using Flame-Ionization Detectors," EPA-600/4-75-010, September
     1975; J.  W. Harrison,  M.  L.  Timmons,  R.  B. Denyszyn, and C. E. Decker, "Evalua-
     tion  of the EPA  Reference Method for  the Measurement of Nonmethane Hydrocarbons
     - Final Report,"  EPA-600/4-77-033,  June 1977.

13.  J. R. Martinez,  F.  L.  Ludwig,  and  C.  Maxwell, "1978 Houston Oxidant Modeling
     Study, Volume I:  Data  Evaluation and  Analysis," March 1982, (SRI Project No.
     7938) p.  57ff.
                                       -44-

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse betore con pictinz;
1 REPORT NC 2. |3. RECIPIENT'S ACCESSION NO
EPA-450/4-83-017
1. TITLE AND SUBTITLE 5. RE
Analysis Of Organic Compound Data Gathered During
1980 In Northeast Corridor Cities S-FE
7. AUTHOR(S) 8. PE
Harold G. Richter
PORT DATE
RFORMING ORGANIZATION CODE
RFORMING ORGANIZATION REPORT \iO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS ! 10. PROGRAM ELEMENT NO.
Office Of Air Quality Planning And Standards
U . S. Environmental Protection Agency 11. c
Research Triangle, NC 27711
12. SPONSORING AGENCY NAME AND ADDRESS 13. T
14. Sf
15. SUPPLEMENTARY NOTES
ONTRACT GRANT NO.
YPE OF REPORT AND PERIOD COVERED
'ONSORING AGENCY CODE

16. ABSTRACT
During the summer of 1980, an extensive monitoring proiect was carried out
as part of the Northeast Corridor Regional Modeling Project (NECRMP) , the primary
purpose of which was to compile an air quality and meteoroloeical data base for use
in photochemical models. Since most of these models require ambient concentrations
of organic compounds as part of the input information, one of the principal efforts
of the study was to collect samples of air from major urban areas of the Corridor
and to analyze them for their organic species composition.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS b. I OENTI Fl E RS. OPEN EN
1

2C SEC.s T. c.-S; .-•

DED TERMS C. COSATI 1 idd'fjruup
i
aR..p.r: :1 ;-^.,f r-ES
'-' •"-'-'-' ' - - ''^ - =-

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                                                          INSTRUCTIONS

   1.    REPORT NUMBER
        Insert the EPA report number as it appears on the cover of the publication.

   2.    LEAVE BLANK

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        Include ZIP code.

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        Indicate interim final, etc., and if applicable, dates covered.

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        Enter information not included elsewhere but useful, such as:  Prepared  in cooperation with, Translation of, Presented'at conference of,
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        Include a brief (200 words or less) factual summary of the most significant information contained in the report. If the report Contains a
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   17.  KEY WORDS AND DOCUMENT ANALYSIS
        (a) DESCRIPTORS - Select from the Thesaurus of Engineering and Scientific Terms the proper authorized terms that identify the major
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EPA Form 2220-1 (Rev.  4-77) (Reverse)

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