v>EPA
              United States
              Environmental Protection
              Agency
             Environmental Monitoring and Support EPA-600 4-79-033
             Laboratory            May 1 979
             Research Triangle Park NC 27711
              Research and Development
Los Angeles
Catalyst Study
              Annual Report

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and  application of en-
vironmental technology.  Elimination  of traditional grouping  was  consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.  Environmental  Health Effects Research
      2.  Environmental  Protection Technology
      3.  Ecological Research
      4.  Environmental  Monitoring
      5.  Socioeconomic Environmental Studies
      6.  Scientific  and Technical Assessment Reports (STAR)
      7.  Interagency Energy-Environment Research and Development
      8.  "Special" Reports
      9.  Miscellaneous Reports

This report has been assigned to the ENVIRONMENTAL MONITORING  series.
This series describes research conducted to develop new or improved methods
and  instrumentation for the identification and  quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants  in the environment
and/or the variance of pollutants  as a function of time or meteorological factors.
 This document is available to the public through the National Technical Informa-
 tion Service, Springfield, Virginia 22161.

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          LOS ANGELES CATALYST STUDY

                 ANNUAL REPORT
                      by

                 Gary F. Evans
   Statistical and Technical Analysis Branch
                     and

             -  Charles E. Rodes
        Environmental Monitoring Branch
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
      OFFICE OF RESEARCH AND DEVELOPMENT
     U.S. ENVIRONMENTAL PROTECTION AGENCY
 RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711

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                                  DISCLAIMER
     This report has been reviewed by the Environmental Monitoring and
Support Laboratory, U.S. Environmental Protection Agency, and approved
for publication.  Mention of trade names or commercial products does
not constitute endorsement or recommendation for use.
                                      n

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                                  FOREWORD

     Measurement and monitoring research efforts are designed to anticipate
potential environmental problems, to support regulatory actions by developing
an  in-depth understanding of the nature and processes that impact health and
the ecology, to provide innovative means of monitoring compliance with regu-
lations and to evaluate the effectiveness of health and environmental pro-
tection efforts through the monitoring of long-term trends.  The Environmental
Monitoring and Support Laboratory, Research Triangle Park, North Carolina,
is responsible for development of:  environmental monitoring technology and
systems; agency-wide quality assurance programs for air pollution measurement
systems; and technical support to the Agency's operating functions including
the Office of Air, Noise and Radiation, the Office of Toxic Substances and
the Office of Enforcement.

     The Environmental Monitoring and Support Laboratory, Research Triangle
Park, North Carolina, has conducted the Los Angeles Catalyst Study since
June 1974, before the introduction of the 1975 model year catalyst equipped
automobiles.  Through a combination of careful site selection and study
design, best-technology sampling equipment, experienced personnel, and a
carefully created quality assurance program, an extensive and reliable data
base has been generated for a multitude of ambient pollutants relating to
automotive emissions.  The Los Angeles Catalyst Study site has also proved
to be an excellent location for evaluating the performance parameters of the
newer methods applied to the measurement of catalyst emission products.
                                                Thomas R. Hauser
                                                    Director
                                         Environmental Monitoring and
                                              Support Laboratory

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                                 ABSTRACT

     This report is a summary of the data collected at the Los Angeles
Catalyst Study (LACS) from June 1974 through December 1977.  Previous
reports of the LACS data were presented at the symposium held in April 1977,
covering the data through 1976.  The current report follows the same data
presentation format, showing 6-month average trends of the summer seasons
(April through September) beginning in 1974.  Additional graphs are included
in this report giving more detailed comparisons of freeway pollutant contri-
butions with traffic parameters.  Also included are method comparisons of
high volume and membrane samplers for total mass, S07, Pb, and ratios of
S/S04 and Pb/Br.                                    *
                                     iv

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                                  CONTENTS

                                                                        Page

Foreword	iii

Abstract	iv

Figures	vi

     1.   Introduction  	   1
     2.   Conclusions   	   6
     3.   Results and Discussion	   8
               Meteorological Conditions, Effects and Trends 	   8
               Traffic  Conditions, Effects and Trends   	  19
               Pollutant Trends (Background and Freeway Contributions)  .  39
               Linear Comparisons  	  57

References	85

Appendix	86

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                                  FIGURES

Number                                                                  Page

 1   Site Locations in Los Angeles	   2
 2   Aerial View of Sampling Sites  	   3
 3   LACS Study Site Composition and Elevation 	   4
 4   Percent Frequency and Speed by Wind Direction 	   9
 5   Frequency of Sea Breeze, Diurnal Pattern (Summer) 	  11
 6   Frequency of Sea Breeze, Diurnal Pattern (Winter) 	  12
 7   Temperature by Hour (Summer/Winter) 	  13
 8   Relative Humidity by Hour (Summer/Winter) 	  14
 9   Carbon Monoxide by Wind Direction 	  16
10   Carbon Monoxide by Wind Speed for Wind Direction - Southwest  ...  17
11   Carbon Monoxide by Hour (Summer)	18
12   Carbon Monoxide by Hour (Winter)	20
13   Sea Breeze Frequency Trend (All Hours/15-18 Hours)  	  21
14   Wind Speed Trend (All Hours/15-18 Hours)  	  22
15   Ambient Temperature Trend (All Hours/15-18 Hours) 	  23
16   Ambient Relative Humidity Trend (All Hours/15-18 Hours) 	  24
17   1976 Weekday Composite Traffic Pattern  	  26
18   1977 Weekday Composite Traffic Pattern  	  27
19   1976 Friday Composite Traffic Pattern	•  28
20   1977 Friday Composite Traffic Pattern 	  29
21   1976 Saturday Composite Traffic Pattern 	  30
22   1977 Saturday Composite Traffic Pattern 	  31
23   1976 Sunday Composite Traffic Pattern 	  32
24   1977 Sunday Composite Traffic Pattern 	  33
25   Percent Catalyst Cars - LA County	34
26   A (C-A) Carbon Monoxide by Hour (Weekday/Weekend)	35
27   Carbon Monoxide by Hour (Freeway Median)	37
28   A (C-A) Pb Concentrations vs Average Traffic Speed  	  38
29   CO Trend (All Hours)	40
30   CO Trend (15-18 Hours)	41
31   NO Trend (All Hours)	42
32   NO Trend (15-18 Hours)  	  43
33   NO? Trend (All Hours)	45
34   NO, Trend (15-18 Hours)	46
35   0/Trend (All Hours)	47
36   Of Trend (15-18 Hours)	48
37   T5P Trend (Hi-Vol, 0-23 Hours)	49
38   TSP Trend (Hi-Vol, 15-18 Hours) 	  50
39   TSP Trend (Membrane, 15-18 Hours) 	  51
40   Pb Trend (Hi-Vol, 0-23 Hours)	52
41   Pb Trend (Hi-Vol, 15-18 Hours)  	  53
                                     VI

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Number                                                                   Page

42   Pb Trend (Membrane, 15-18 Hours)   	   54
43   S0d Trend (Hi-Vol, 0-23 Hours)	   55
44   SO? Trend (Hi-Vol, 15-18 Hours)  	   56
45   SO? Trend (Membrane, 15-18 Hours)  	   58
46   NH? Trend (Hi-Vol, 0-23 Hours)	   59
47   NO- Trend (Hi-Vol, 0-23 Hours)	   60
48   SOp Trend (Bubbler, 0-23 Hours)	   61
49   Membrane TSP vs Hi-Vol TSP (Site A, 4-Hour)	   63
50   Membrane TSP vs Hi-Vol TSP (Site C, 4-Hour)	   64
51   Membrane TSP vs Hi-Vol TSP (Site B, 24-Hour)	   66
52   Membrane TSP vs Hi-Vol TSP (Site D, 24-Hour)  	   67
53   Membrane Pb vs Hi-Vol Pb (Site A, 4-Hour)	   68
54   Membrane Pb vs Hi-Vol Pb (Site C, 4-Hour)	   69
55   Membrane Pb vs Hi-Vol Pb (Site B, 24-Hour)  	   70
56   Membrane Pb vs Hi-Vol Pb (Site D, 24-Hour)	   71
57   Membrane SO, vs Hi-Vol SO, (Site A, 4-Hour)	   72
58   Membrane SO, vs Hi-Vol SO? (Site C, 4-Hour)	   73
59   Membrane SO? vs Hi Vol SO? (Site B, 24-Hour)	   74
60   Membrane SO? vs Hi Vol SO? (Site D, 24-Hour)	   75
61   Membrane S Vs Hi-Vol SO, (Site A, 4-Hour)	   76
62   Membrane S vs Hi-Vol SO? (Site C, 4-Hour)	   77
63   Membrane S vs Hi-Vol SO? (Site B, 24-Hour)	   78
64   Membrane S vs Hi-Vol SO? (Site D, 24-Hour)  	   79
65   Membrane Pb vs Membrane Br (Site A, 4-Hour)	   81
66   Membrane Pb vs Membrane Br (Site C, 4-Hour)	   82
67   Membrane Pb vs Membrane Br (Site B, 24-Hour)  	   83
68   Membrane Pb vs Membrane Br (Site D, 24-Hour)	   84

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                                   SECTION 1

                                 INTRODUCTION

     The Los Angeles Catalyst Study (LACS) was established in the summer of
1974 to assess the impact of catalytic converters on air quality.  Several
previous LACS reports were presented at a symposium in April  1977 and compiled
in an EPA technical document, The Los Angeles Catalyst Study Symposium.
That report details the rationale behind the site selection,  pollutant and
measurement technique selection, and data presentation format.   The current
report highlights the sampling philosophy and updates the data  through
December 1977.  Trends are described and selected methods compared.

     The location of the monitoring sites on the San Diego Freeway in Los
Angeles is shown in Figure 1.  At this location the freeway is  6.5 kilometers
from the Pacific Ocean and approximately parallel to the coast  line.   The
terrain near the freeway is relatively flat as can be seen in the photograph
in Figure 2, which identifies monitoring Sites A, B, C, and D.   The freeway is
approximately 2 meters above grade as shown in the elevation diagram in  Figure
3, and all sampling inlets are raised to 1 meter above the freeway grade.

     The sampling equipment currently operated at the LACS sites is also
indicated in Figure 3.  Sites A and C are fully instrumented with aerosol and
gas samplers.  Sites B and D contain only aerosol samplers.  Using extended
sampling lines, the carbon monoxide (CO) at Site B is monitored from Site A,
and the CO in the center of the freeway is monitored at Site C.  All  meteor-
ological data are collected at 10 meters elevation at Site A, while all
traffic speed and count data from the freeway are monitored by  a computer
controlled data system at Site C.  Additional monitors generate hourly
averages for NO, N0? and 03 concentrations.  Total sulfur monitoring was
discontinued in the fall of 1977 because the extremely low sulfur levels
(typically <20yg/m ) were near the operating threshold for the  instruments.
Integrating samplers include standard high volume (hi-vol) samplers operated
at 1.4 ro/min. with glass fiber filters, low volume membrane samplers
(0.14 m^/min.) using cellulose ester filters and dichotomous samplers
(0.14 m /min).  Two types of aerosol size fractionating samplers have been
operated at the LACS.  The Anderson 5-stage cascade was operated until the
fall of 1977.  The 3-stage massive volume impactor developed by Battelle is
operated to collect large (>1 gram) aerosol samples for health screening
studies.

     Integrating samplers are operated on both a midnight-to-midnight and
3 to 7 p.m. basis.  The latter 4-hour time period coincides with peak traffic
volume and meteorological conditions favorable to the detection of the freeway
contribution of air pollutants.  Since differences between upwind and downwind

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                 337.5'
NW
                                                                                     112.5°
                     /
                    /
                  /
                 /
               202.5°
1
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                                                                            SE
                      Figure 1.  Site location in Los Angeles.

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Figure 2.   Aerial  view of sampling sites.

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                             PREVAILING WIND
                                                        SAN DIEGO
                                                        FREEWAY SURFACE-


                                                       i     n         1
                                                      2m ABOVE GRADE
                                                      T
                                                                 SEPULVEDA BLVD
SITE A

CO ANALYZER
TOTAL SULFUR (S02) ANALYZER
NO/NO, ANALYZER
03 ANALYZER

24-HR S02 BUBBLER

24-HR HI-VOL
4-HR HI VOL (37 PM)
4-HR MEMBRANE (3-7 PM)
24-HR CASCADE
MASSIVE VOLUME AIROSOt SAMPlEfi
24-HR DICHOTOMOUS SAMPLER

AMBIENT TEMP. AND DEWPOINT
WIND SPEED
WIND DIRECTION
SITES

24-HR HI-VOL
 4-HR HI-VOL (3-7 PM)
24-HR MEMBRANE
SITEC

CO ANALYZER
TOTAL SULFUR (SO,) ANALYZER
NO/NO? ANALYZER
03 ANALYZER

24-HR S02 BUBBLER

24-HR HI-VOL
4-HR HI-VOL (3-7 PM)
4-HR MEMBRANE (3-7 PM)
24-HR CASCADE
MASSIVE VOLUME AEROSOL SAMPLER
24-HR DICHOTOMOUS SAMPLER

TRAFFIC SPEED AND COUNT SYSTEM
SITED

24-HR HI-VOL
 4-HR HI-VOL (3-7 PM:
24-HR MEMBRANE
                            Figure 3.   LACS study site composition and elevation.

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measurements are the basis for determining the freeway contribution, the wind-
speed and direction are very  important ancillary measurements.

     Data from the continuous samplers are collected on strip charts which are
subsequently electronically digitized to obtain hourly averages.  The inte-
grated samples collected on-site are sent to the contractor's (Rockwell Air
Monitoring Center) laboratory for subsequent analyses.  Membrane samples are
also sent to Lawrence Berkeley Laboratory (LBL) for X-Ray Fluorescence (XRF)
elemental analyses.  The data are transmitted to EPA/RTP on magnetic tape in
SAROAD  format for processing and interpretation.

     In order to maintain data quality, a comprehensive Quality Assurance
Program is maintained during  the sampling and analysis following the guide-
lines in the EPA Quality Assurance Handbook.   The sampling QA program includes
checks and calibrations of flowrates and pollutant measurements.  The labora-
tory QA program includes routine unknown (spiked) samples sent to the con-
tractor's laboratory as well  as samples split with the EPA reference laboratory
at RTP to verify comparability.

     The current validated data set contains approximately 500,000 continuous
monitor hourly averages and 180,000 analysis values on integrated aerosol
samples.  The data are examined by EPA for long term trends, effects of
parameters such as meteorology and traffic flow on pollutant data, and inter-
comparison of methods.  Because the data base is large and varied a contract
was awarded to the University of Wisconsin's Department of Statistics (68-02-
2261) to examine the LACS data and, through various techniques such as time
series modeling, quantify the trend results and explore perturbations in the
data.  Some of the key results from this contract are also presented in this
report.

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                                 SECTION 2

                                CONCLUSIONS

     t  The LACS site continues to provide favorable meteorological and
traffic conditions for the determination of the freeway contribution to
ambient concentrations of air pollutants.  This is especially so during
summer months and between the hours of 3-7 p.m.

     •  There has been virtually no change in the distribution of wind
directions since the beginning of the study.  Average summer wind speed,
however, has decreased ten percent since 1975 and the resulting decrease
in dilution air may have contributed to a slight inflation in apparent
freeway contribution to air pollutant concentrations.

     •  The opening of a fifth northbound lane in February 1977 resulted in
a ten percent increase in weekday northbound traffic volume and, perhaps
more significantly, an increase in 3-7 p.m. average weekday northbound
speed from 25 to 45 mph.  This change produced a dramatic impact on 3-7 p.m.
concentrations of pollutants, especially Pb.  Southbound and weekend
traffic patterns exhibited very little change.

     •  The proportion of vehicle miles driven on the San Diego Freeway
by catalyst-equipped vehicles reached an estimated 43 percent in December 1977.

     •  Carbon monoxide measurements made in the center of the freeway
average twice the corresponding concentration observed at the near downwind
location (Site C).

     •  The background concentrations of CO, NO, N02» 0.,, TSP (except
4-hour membrane measurements) and Pb have remained essentially constant
since monitoring commenced.

     t  Background levels of SO, decreased sharply in 1976 followed by a
slight increase in 1977 while the background level of S02 exhibited a marked
increase in 1977.

     t  The freeway contribution of CO, TSP and Pb has rnrt decreased to the
extent expected since the introduction of the catalyst with the 1975 model
vehicles.   Rapid decrease in catalyst efficiency with accumulated mileage,
reported increases in the improper usage of leaded gasoline in catalyst
automobiles and changes in the traffic flow patterns at the LACS may all
have contributed to this observation.

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     t  The freeway contribution of NO and N0? has increased significantly
through the study period.

     •  The freeway contribution of SO,  (4-hour membrane measurements, only)
appears to have increased slightly, but  still represents only a minor incre-
ment ('vlyg/m ) above background levels.  The freeway contribution of S02,
meanwhile, has not decreased significantly.

     •  Linear comparisons between collocated high volume and membrane
samplers reveal that while the overall TSP agreement is unsatisfactory, there
is very good agreement for 4-hour and 24-hour Pb measurements.

     •  Four-hour SO, measurements from  high volume samplers, thought to be
inflated by artifact formation, do not compare well with simultaneous
membrane measurements.  Twenty-four-hour SO, measurements, however, exhibit
very strong correlation and excellent agreement between the two sampling
methods.

     •  Comparison of membrane S and SO, results suggest that virtually all
of the aerosol S observed at the LACS sites exists in the SO, form.

     «  Comparison of membrane Pb and Br results suggest that almost all
of the Pb observed at the LACS sites is  automobile-generated.

     •  A method to normalize contribution measurements based upon
meteorology and traffic effects needs to be developed in order to improve
the analysis of trends in the LACS data  base.

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                                 SECTION 3

                          RESULTS AND DISCUSSION

METEOROLOGICAL CONDITIONS, EFFECTS AND TRENDS

     The configuration of the sampling sites for the Los Angeles Catalyst
Study  (LACS) is shown in Figure 1.  The four primary sites are situated
along  a line perpendicular to the San Diego Freeway with two sites on
either side.  Through this part of the Los Angeles basin, the freeway runs
roughly parallel to the Pacific Ocean (i.e., southeast to northwest) at a
distance of approximately 6.5 kilometers inland.  The freeway perpendicular,
serving as the site line, occurs at 235° (i.e., in the southwest octant).

     Figure 2 is an aerial view of the Veterans Administration Hospital
and cemetery property on which the LACS sites are located.  The figure
indicates the positions of Sites A and B on the ocean (or "upwind") side of
the freeway and C and D on the opposite (or "downwind") side.  As shown in
Figure 3, all of the continuous monitoring equipment is located at Site A
(30 meters upwind of the freeway) and/or Site C (8 meters downwind).  In
addition, some carbon monoxide measurements have been made at the freeway
median and at a remote site located 230 meters from the freeway on the up-
wind side.

     Wind direction and speed have been continuously monitored since the
beginning of the LACS (June 1974) by means of a anemometer located at Site A
at an  elevation of 10 meters.  Figure 4 depicts the distribution of occur-
rences and the associated average windspeed  as a function of wind direction.
Wind direction strip charts are reduced to hourly averages and reported to
the nearest ten degrees.  Thus, there are 36 possible values for wind
direction plus the classification 'calm'  (denoted by zero)'which is used for
any hour for which the accompanying windspeed is less than one mile per hour.
The lower curve in Figure 4 is a frequency distribution of all the wind
direction data collected at Site A since the beginning of the study.  It was
plotted by tabulating the number of hours of occurrence for each possible
wind direction, dividing by the total number of hours for which valid wind
direction data are available and expressing the quotients as percentages.
The upper curve is the average windspeed over all hours for which the winds
were from the indicated direction.

     Prevailing wind direction was one of the prime considerations involved
in the selection of a suitable site for the LACS.  Areas of the Los^Angeles
basin  which are close to the ocean are characterized by an alternating
pattern of onshore (or "sea breeze") winds during the daylight hours and
offshore (or "land breeze") winds during the dark hours.   Thus, it was felt
that a major freeway running parallel and near to the ocean would provide

                                      8

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               Figure 4.  Percent frequency and speed by wind direction (all data).

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the desirable property of prevailing winds which were perpendicular to the
freeway for a large portion of almost every day.  Such a wind pattern
would enable the detection of the freeway contribution to ambient levels
of air pollutants by differencing simultaneous measurements taken upwind
and downwind of the freeway.

     As shown in the lower curve in Figure 4, wind direction at the LACS
site follows a bimodal distribution with two distinct patterns:  a sea breeze
pattern centered in the southwest octant with tails in the south and west
and a somewhat more diffuse land breeze pattern centered in the north with
tails in the northwest and northeast.  The upper curve in Figure 4 shows
that the sea breeze mode (wind directions from the south, southwest and west)
is accompanied by the highest average windspeeds.

     Since the sea breeze mode provides the most favorable conditions for the
detection of pollutant sources on the freeway, it is useful to look at the
diurnal and seasonal patterns in the occurrence of winds from this sector.
Figure 5 shows the percentage occurrence of sea breeze by hour-of-day for all
summer months (defined as April through September, inclusive).  In the early
morning hours, winds are typically light and variable and are out of the
sea breeze sector (S+SW+W) for only about 20% of all summer days.  Following
sunrise (about 7 a.m.) the wind pattern begins to shift into the sea breeze
mode and from noon until 7 p.m. winds are nearly always from this sector.

     Since the LACS integrated samplers are operated on either a 24-hour basis
(midnight to midnight) or a 4-hour basis (3-7 p.m.), the overall percentage
occurrence of sea breeze for each of these intervals is shown in the figure
(61% and 97%, respectively).  This suggests that while the 4-hour afternoon
sampling interval should provide a good measure of the freeway contribution to
pollutant concentrations, the 24-hour interval will likely be an underestimate
since the diurnal wind pattern is such that all sites will be impacted by the
freeway during some portion of the day.

     Figure 6 shows the diurnal pattern of sea breeze for winter months
(October through March).  While similar to the summer pattern, the figure
shows that the period of favorable meteorology is of much shorter duration
because there are fewer hours of sunlight.  Overall, the sea breeze accounts
for only 35% of winter hours and from 3-7 p.m. the percentage sea breeze is
about 65%.  Thus, cross-freeway differences obtained from integrated
samplers would be expected to be notably different between summer and winter
seasons.

     The diurnal pattern for temperature is shown in Figure 7 with separate
curves for the summer and winter seasons.  Temperature follows a symmetrical
pattern reaching its peak in the early afternoon.  The seasonal difference
in temperature is not large (5°F overall average).  Figure 8 provides the
same information for percent relative humidity.  Humidity reaches a minimum
in the early afternoon and averages 5% higher in the summer season.

     To evaluate the impact of meteorology on observed pollutant concentra-
tions, the carbon monoxide data collected at the LACS sites will be examined
in some detail.  Carbon monoxide is particularly useful as a "tracer" of

                                     10

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                                  SUMMER: APR. - SEP.
% FREQ.
(S+SW+W)
           100.
            90.
            80.
            70.
            60.
            SO.
            40.
            30.
       OVERALL AVG. = 61%
          3-7 PM AVG. = 97%
            20.
            10.
                   I	I
I	I
                                                                          i   l   l   I   I   I
                01   234   5  6   7   8   9  10 11  12  13 14 15  16  17 18  19  20 21 22 23
           -10.
 HOUR OF DAY
                                                                    3-7 PM
           -20.
           -30.
           -40.
                       Figure 5.  Frequency of Seabreeze diurnal pattern.

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          100.0
                               WINTER: OCT. - MAR.
% FREQ.
(S+SW+W)
           90.0
           80.0
           70.0
           60.0 -
           50.0
           40.0
30.0
           20.0
           10.0
            0.0
                                                  OVERALL AVG. = 35%
                                                  3-7 PM AVG. = 65%
               0  1  2   3  4   5   6  7  8   9 10  11 12  13  14  15  16 17  18  19 20  21  22  23
          -10.0
                                           HOUR OF DAY
                                                          3-7 PM
          -20.0
         -30.0
         -40.0
                        Figure 6.  Frequency of Seabreeze diurnal pattern.
                                             12  :

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AVO. - 0»*f
AVO.
                                  It  i. U U  U to U  U  k
         183
                                 HOUR OP GAY
                                                      I-
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                          Figure 7, Temperature by hour.
                                       13

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of
   100.
    90.
    80.
    70.
    60.
    SO.
    40.
    30.
    20.
    10.
i  B  y  n   n—a
       O SUMMER: APR. - SEP.
       D WINTER: OCT. - MAR.
                                  I
AVG. = 68%
AVG. = 63%
                                                      I	I
   -10.
   -20.
   -30.
   -40.
01   23      56   78  9   10  11  12  13  14 15  16 17  18 19  20  21  22 23

                           HOUR OF DAY             3-7 PM
                          Figure 8.  Relative humidity by hour.
                                           14

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pollutant behavior because it is an inert, automobile-generated pollutant
and has been continuously monitored since June 1974 at both Sites A and C.
Inlet probes are at an elevation of about one meter above freeway grade
(i.e., approximately at commuter elevation).

     Figure 9 shows CO concentrations at Site A (Symbol "A"),  Site C
(Symbol "C"), and the cross-freeway (C-A) difference (Symbol "A") as a
function of wind direction.  The plots were constructed using all valid CO
data since the beginning of the study, stratifying by wind direction and
computing average concentrations by site and the average concentration
difference (C-A) for each wind direction.  It is interesting to note that
when winds are calm (wind direction = 0), Site C exceeds Site A by about one
part per million (1 ppm) due to a proximity effect (Site C is 8 meters from
the freeway while Site A is 30 meters from the freeway).  The cross-freeway
difference (C-A) curve is slightly (<1 ppm) negative (A exceeding C) when
winds are from the north, northeast or east.  It crosses the zero line when
winds are along the freeway parallels (southeast or northwest) and is
distinctly positive when winds are from the sea breeze mode (south, southwest
or west), reaching a maximum of about 5 ppm when winds are from the southwest
(i.e., directly perpendicular to the freeway).  This pattern confirms the
utility of the study design in making use of the naturally occurring sea-
breeze to separate emission products from background levels of automobile-
generated pollutants.

     In an attempt to investigate the effect of windspeed on pollutant
concentrations, the CO data base was first sorted for all hours when the
prevailing wind direction was from the southwest (since these essentially
perpendicular winds give rise to the largest cross-freeway differences).
The restricted data base was then further stratified on the basis of wind-
speed intervals, and the average CO concentrations at Site A, Site C and
the freeway difference (C-A) were computed for each interval.  The results
are plotted in Figure 10.  Again, it is observed that the concentration at
Site C substantially exceeds that at Site A even at very light windspeeds due
to the proximity effect.  As windspeed increases, the average CO concentra-
tion decreases at Site A and increases at Site C until windspeed reaches
about 4.5 mph.  Above this speed, the average CO concentration at both sites
and the cross-freeway difference decrease due to the effect of increased
dilution.

     Figure 11 shows the diurnal pattern in CO concentration for each site and
the cross-freeway difference as a composite of all summer months.  The cross-
freeway difference is very small during early morning hours but  begins to
build at about 7 a.m. as the sea breeze mode begins to predominate and the
morning traffic rush hour period begins.  It levels off at  about noon when the
sea breeze mode is well established and the morning rush hour period  subsides.
Then at about 3 p.m. the cross-freeway difference increases again  in  response
to the afternoon rush hour period, reaching a diurnal maximum of about  6  ppm
at 5 p.m.  It is worth pointing out that the 3-7 p.m. sampling  interval  for
integrated samplers appears to cover the optimum period  for the  detection  of
emission sources on the freeway.
                                      15

-------
CONC

(PPM)
            6.99
            6.29
           5.59
           4.87
           4.17
           3.47
           2.75
           2.05
           1.35
           0.55
          -0.05
          -0.75
                   1   I   1
                                                                                                                  '•^
      1  1  1  1  I  I   I   1  I   I      I   I   I  I   I   I   I   I   I  I   I   II   I   1  I   I   I   I  I
               o  o
                <•
                u
                    N
                              S  S
NE
              8  I  ?
        CM M  *T §>
S  §
                                                                Degrees
2  8
«M  «M
                                                   p*  CD O)

                                                   CM  CM Kl
E           SE           S           SW          W



 Figure 9.  CO by wind direction (all data).
o  o  o

pi  n  m
                                                                                                                    n
                                                                                                         NW

-------
  6.0 —
  5.0 —
  4.0 —

CO
(PPM)

  3.0 —
  2.0 —
  1.0 -
              "1	1	T	«        I	—1	1-
               1.0      2.0      3.0      4.0      5.0      6.0       7.0
                                         WIND SPEED (MPH)
T
 8.0
9.0
10.0
                                   A  - AVG. CO CONCENTRATION AT SITE A

                                   C  - AVG. CO CONCENTRATION AT SITE C

                                   A  - AVG. CO CONCENTRATION DIFFERENCE (C-AI
                                    Figure 10.  CO by wind speed for WD=SW.

-------
                           SUMMER: APR. - SEP.
        10.0 -
         9.0 -
         8.0 -
         7.0 _
CONC    6.0
(PPM)
            01   234  5   6  7  8   9  10  11  12  13 14 15  16 17 18  19 20  21  22   23
       -2.0
       -3.0
       -4.01
D INDICATES SITE C
• INDICATES SITE A
•*• INDICATES DIFF. (C-A)
AVG« 4.5 PPM
AVG- 1.8 PPM
AVG- 2.8 PPM
                          Figure 11.  Carbon monoxide by hour.
                                            18

-------
     Figure 12 shows the  CO diurnal  pattern as a composite of all winter
months (October through March).  Though  similar in pattern to the summer
months, the winter pattern is  strongly affected by the shorter duration of the
sea breeze mode.  By 7 p.m. the cross-freeway difference in CO concentration
has practically disappeared for the  average winter day.

     Figure 13 depicts the average percentage sea breeze occurring during
each of the four  summer seasons since the  beginning of the study.  The
averages are computed on  both  a 24-hour  and a 4-hour  (1500-1800 hours)
basis to conform  to the intervals of operation of integrated samplers.  As
the figure shows, sea breeze accounts for  virtually all summer hours during
the 4-hour afternoon sampling  period and for about two-thirds of all
summer hours on a 24-hour basis.  There  has been no apparent trend in the
occurrence of sea breeze  over  the four years of the study.

     Figure 14 is a similar plot for summer windspeed data.  In addition
to the seasonal average,  the 95th percentile value is included in the 24-
hour plots to give some indication of the  upper tail of the distribution.
As previously noted, afternoon (sea  breeze) winds tend to be stronger than
the average for the entire day.  In  addition, average windspeed increased
slightly in 1975  and has  subsequently decreased to the 1974 average level.
Since decreased windspeed provides less  dilution air, this trend may have
the effect of slightly increasing the apparent freeway contribution of air
pollutants (see Figure 10).

     Ambient temperature  and percent relative humidity have been collected
continuously at LACS Site A since October  1974.  Summer season temperature
and humidity data are shown in Figures 15  and 16, respectively.  The high
relative humidity in the  summer of 1977  should be noted.

TRAFFIC CONDITIONS, EFFECTS AND TRENDS

     The LACS traffic count and speed system became operational in September
1976.  The system consists of  inductive  loops embedded in each of the ten
lanes of the San  Diego Freeway, an interface system to convert electric
impulses from the loops to digital counts  and a minicomputer located in the
shelter at Site C to store traffic count data on magnetic tape.  Operating on
a ten-minute cycle, the system provides  a  total vehicle count for each lane
and within each of six speed categories:   0-25, 25-35, 35-45, 45-55, 55-65
and greater than  65 miles per  hour (mph).  Every two  weeks, the magnetic  tape
from the on-site  computer is forwarded to  Research Triangle Park, North
Carolina (RTF) where the  data  are reduced  to hourly traffic volume and esti-
mated average speed northbound and southbound.

     Initially, only eight freeway lanes were open to traffic  (four  lanes
northbound and four lanes southbound).   In February 1977,  a fifth northbound
lane was opened and the marked consequences of that change will  be  discussed
later in this section.

     Since no statistically significant  day-of-week differences  appear  for
the composited Monday through  Thursday data, these  days may be  pooled into


                                      19

-------
                       WINTER: OCT. - MAR
       10.0  -
        9.0 -
        8.0 -
        7.0 -
CONC   6.0
(PPM)

        5.0 -
        4-0 -
        3.0
        2.0 -
        0.0
       -1.0
       -2.0
       -3.0
            3-7 PM
                                      HOUR OF DAY
       -4.0
                       D  INDICATES SITE C
                       •  INDICATES SITE A
                       A  INDICATES DIFF  (C A)
AVG= 4.7 PPM
AVG= 3.4 PPM
AVG= 1 3 PPM
                          Figure 12.  Carbon monoxide by hour.
                                            20

-------
5-
c

-------
-d
o>
01
ex
•o
c
*r~
3
          Summer

           1974
    Summer = April thru September
                    Summer

                     1978
Summer

 1979
0-2300 Hr.
                                                     -95th Percent!le


                                                     -Arithmetic Mean
            1500-1800  Hr.
         Figure 14.  LACS trend data. Wind speed (interval comparison).
                                               22

-------
    100

     90

     80

     70
 2>  60
     50

     40

     30

     20

     10

      0
                               I      I      I     I
           Summer
            1974
Summer
 1975
Summer      Summer     Summer     Summer
 1976        1977       1978       1979
               •  -95th Percent-He
Summer  = April thru September
                0-2300 Hr.
                                                     -Arithmetic Mean
                                                                                1500-1800 Hr.
         Figure 15.   LACS trend data. Ambient temperature (interval comparison).
                                             23

-------
                                                            Summer
                                                             1979
Summer = April thru September
                                0-2300 Hr.
   1"
*-i-A
-95th PercentHe

-Arithmetic Mean
                       n
1500-1800 Hr.
   Figure 16.  LACS trend data. Ambient relative humidity (interval comparison).
                                       241

-------
     Figures 17 and  18 depict  the weekday diurnal traffic patterns for
September through December  1976  and  for the same period in 1977   Traffic
volume follows a bimodal  pattern reaching peaks at about 7 a.m. (morning
rush period) and again at about  4 p.m. (afternoon rush period).  The
southbound lanes exhibit  the larger  peak during the morning rush period
while northbound lanes exhibit the larger peak during the afternoon rush
period.  This observation is consistent with the fact that the LACS location
is northwest of downtown  Los Angeles and, thus, the weekday traffic burden
shifts from southbound in the  morning to northbound in the afternoon.
Traffic speed averages about 55  mph  but congestion causes it to dip somewhat
during the morning and afternoon rush periods.

     A comparison of Figure 17 with  Figure 18 reveals that while southbound
traffic was virtually unchanged  from 1976 to 1977, the northbound patterns
changed significantly in  response to the opening of the fifth lane.  North-
bound traffic count  increased  approximately 10% with most of the increase
taking place during  the two rush periods.  In addition, the minimum average
hourly traffic speed (i-e., the  afternoon rush hour speed) exhibited an
increase from 18 mph in 1976 to  43 mph in 1977.  Apparently traffic volume
northbound on the freeway in the afternoon had been approaching capacity and
the opening of the fifth  lane  has reduced congestion to a considerable
extent enabling an increase in traffic volume and average speed.

     Friday consistently  carries the heaviest traffic volume of the week on
the San Diego Freeway at  the LACS.   The diurnal traffic patterns for Friday
in the fall of 1976  and 1977 are shown in Figures 19 and 20, respectively.
The year-to-year changes  are similar to those discussed for the weekday
traffic patterns.

     Figures 21 through 24  display the diurnal traffic patterns by year for
Saturdays and Sundays.  As  expected, the patterns for weekend do not show
the characteristic morning  and afternoon rush period effects, average speed
remains fairly constant throughout the course of the day and overall traffic
volume is considerably less than that for weekdays.  Except for an overall
increase of about 5% in northbound traffic, there was little change between
the two years in weekend  traffic patterns.

     In Figure 25, the percentage of vehicle miles driven by catalyst
equipped cars in Los Angeles County  is presented as a function  of  time.   The
curve was generated  by Rockwell  Air  Monitoring Center from  county  sales
registration data adjusted  to  reflect actual vehicle miles  driven  as a
function of model year.   This  curve  indicates that catalyst equipped vehicles
accounted for approximately 43%  of vehicle miles traveled as of December  1977,

     To illustrate the impact  of changing traffic conditions upon  pollutant
concentrations, it is useful to  return to the example of  carbon monoxide.
In Figure 26, the cross-freeway  difference  (C-A)  in  CO  concentration is
plotted to contrast  the difference  in  the diurnal pattern  between  weekdays
(Monday through Friday) and weekends (Saturday and  Sunday).   The impact of


                                     25

-------
                                    I      I     I

                                        NORTHBOUND AVERAGE =  96785
                        I      I      I      I      II     i
                                                                         0

0   2.00  4.00  6.00  8.00  10.00  12.00 14.00 16.00 18.00 20.00 22.00 24.00

                                                                         80
                                    I      I     I     I     1      I



                                        SOUTHBOUND AVERAGE =  93981     J
      II            I      I      I
                                                                            o
                                                                            UJ
                                                                            LU
                                                                            a.
70




60




50




40




30




20




10
0   2.00  4.00  6.00  8.00   10.00  12.00 14.00 16.00 18.00 20.00 22.00 24.00

                                  TIME

 SPEED  (MPH)   —ft—   TRAFFIC COUNT  (AVE)          TOTAL AVERAGE COUNT = 190766


          Figure 17.  LACS traffic data.  1976 Weekday composite.

                     Monday- Thursday (42 days).


                               •   26

-------
80  -
                     I      ,	,	,	
                   NORTHBOUND  AVERAGE =  106443
   0   2.00  4.00  6.00  8.00  10.00 12.00 14.00  16.00 18.00 20.00 22.00 24.00
                                             I     I      I      I      I

                                            SOUTHBOUND AVERAGE =  94146    J
                     I      I      I      I      I      I
   0   2.00  4.00  6.00   8.00   10.00  12.00  14.00 16.00 18.00 20.00 22.00 24.00
                                     TIME
    SPEED  (MPH)  —6—   TRAFFIC COUNT  (AVE)          TOTAL AVERAGE COUNT =  200689
           Figure 18.  LACS traffic data.  1977 Weekday composite.
                      Monday- Thursday (29 days).
                                     27

-------
     80
     70  -
     60



Mo   50
 «-i


 o   40
 u.
 u_

 »-   30



     20


     10
                          I     I      I     I      I

                       NORTHBOUND  AVERAGE = 103908
                                                                    I      I
                    I     I     I     I     I      I      I      I      I      I
                                             80


                                             70


                                             60


                                             50


                                             40


                                             30


                                             20


                                             10


                                             0
                                                                                      a.
                                                                                      Q.
                                                                                      CO
        0   2.00  4.00  6.00  8.00  10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00
     80
     70
     60
~o   50
 t—i
 X

 2   40
     30
     20
     10
              I     1
T     I      I      I      I      I     I

          SOUTHBOUND AVERAGE = 100730
              II.    J	I     I     I      I      I      I      I      I
                                                                                  80


                                                                                  70


                                                                                  60


                                                                                  50


                                                                                  40


                                                                                  30


                                                                                  20


                                                                                  10


                                                                                  0
                                                                                     a.
                                                                                     to
        0   2.00  4.00  6.00  8.00  10.00 12.00 14.00 16.00 18.00 20.00'22.00 24.00

                                          TIME

        SPEED (MPH)  —*—  TRAFFIC COUNT  (AVE)          TOTAL AVERAGE  COUNT  =  204637


                Figure 19.   LACS traffic data. 1976 Friday composite (9 days).
                                          28

-------
C\J
 O
  X

 O
 «=c
 cc.
               I      I—I—I
                      NORTHBOUND  AVERAGE  •  114162
                                                                                     O.
                                                                                     CO
         0   2.00  4.00  6.00  8.00  10.00 12.00 14.00 16.00 18.00 20.00  22.00  24.00
                                                 SOUTHBOUND AVERAGE = 100988
                                              I      I      I      I     I      I
         0   2.00  4.00  6.00  8.00  10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00
                                            TIME

         SPEED  (MPH)   —a—  TRAFFIC COUNT (AVE)          TOTAL AVERAGE COUNT = 215151

                  Figure 20.  LACS traffic data.  1977 Friday composite (9 days).
                                           29

-------
                                             I      I      I      I      I

                                           NORTHBOUND AVERAGE  » 94419
                                                                         -  10
                                                                            0
   0   2.00  4.00  6.00  8.00  10.00 12.00  14.00  16.00  18.00 20.00 22.00 24.00
80
                                             I      I      I      i      I


                                           SOUTHBOUND AVERAGE • 89141    _
   0   2.00  4.00  6.00   8.00   10.00  12.00  14.00 16.00 18.00 20.00 22.00 24.00

                                     TIME

   SPEED (MPH)  —o—   TRAFFIC  COUNT  (AVE)          TOTAL AVERAGE COUNT * 183560


          F igu re 21.  LACS traffic data.  1976 Satu rday composite (10 days).
                                     30

-------
     80





     70





     60





^    50
 o
 i-H

 X

 o   40
 »-H
 LL.
 Lu


 §   30





     20





     10
               T	1
T      I	1	1	1	1	T


           NORTHBOUND AVERAGE = 98337
         _L
J - 1
 I
                                             I _ I
_L
                                                        80




                                                        70




                                                        60




                                                        50




                                                        40




                                                        30




                                                        20




                                                        10
                                                                                 Q.

                                                                                 OO
   0   2.00  4.00  6.00  8.00  10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00
80
                                              I      I      I      I     I



                                            SOUTHBOUND AVERAGE = 88682    _J
                            I      I	I	I
                                                                              0

   0   2.00  4.00  6.00  8.00   10.00  12.00  14.00  16.00  18.00 20.00 22.00 24.00


                                      TIME

    SPEED  (MPh)   —£>—  TRAFFIC COUNT (AVE)          TOTAL AVERAGE COUNT =  187019



          Figure 22.  LACS traffic data.  1977 Saturday composite (11 days).



                                      31

-------
                                            NORTHBOUND AVERAGE = 83581    _
                           I      I      I      I     I     I     I      I
                                                                         -  10
                                                                            0
   0   2.00  4.00  6.00  8.00  10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00
80
                                       I      I     I     I     I     I

                                           SOUTHBOUND AVERAGE = 80782    _
   0   2.00  4.00  6.00  8.00   10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00

                                     TIME

   SPEED (MPH)    —*—   TRAFFIC COUNT (AVE)          TOTAL AVERAGE COUNT = 164364


        Figure 23,  LACS traffic data. 1976 Sunday composite (11 days).
                                     32

-------
                                 I      I	1	1	1	1	1
                                      NORTHBOUND AVERAGE  COUNT  = 88089
   0   2.00  4.00  6.00  8.00  10.00 12.00 14.00  16.00  18.00 20.00 22.00 24.00
80
                                      SOUTHBOUND AVERAGE COUNT  • 81068    _
                            I      I     I      I     I      I
   0   2.00  4.00  6.00  8.00  10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00
                                      TIME
    SPEED (MPH)    —a—   TRAFFIC COUNT (AVE)          TOTAL AVERAGE COUNT = 169157

          Figure 24.  LACS traffic data. 1977 Sunday composite (10 days).
                                     33

-------
 
-------




g
_i
I
PARTS PER





12.0
11.0
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
ok
01  2  3  4  56  7  8  9  10 11 12 13 14  115  16 17 18 19 20 21 22 23
                         HOUR OF DAY
3-7 PM
                               O TOTAL WEEK DAYS



                               Q TOTAL WEEK ENDS







        Figure 26.  CO difference (C-A) weekdays vs. weekends.
                            35

-------
the afternoon rush period is obvious in the plot comparison.

     In February 1977, a probe was placed in the freeway median for the
purpose of obtaining on-freeway measurements of CO concentrations.  The
diurnal pattern in CO concentrations in the freeway median is shown in
Figure 27 for the summer of 1977.  Unlike the patterns observed at Sites A
and C, CO concentrations in the freeway median follow the traffic pattern
quite closely and do not appear to be substantially affected by changes in
wind direction and speed.  In addition, the median concentrations signifi-
cantly exceed the corresponding concentrations observed at the off-freeway
locations (Sites A and C).

     Afternoon (1500-1800 hours) traffic and pollutant data for September
1976 were examined in some detail in an effort to determine the impact of
the change in traffic volume and speed that occurred with the opening of the
fifth northbound lane in February 1977.  The data used in this analysis
appear in Table A-l of the appendix.  The data were initially screened to
insure homogeneous meteorological conditions.  A matrix of cross-correlation
coefficients of the variables involved appears in Table A-2.  The strongest
correlation in evidence is between average traffic speed and A(C-A) Pb
concentrations (r=0.98).

     Several literature articles have discussed the relationship between
average vehicle speed and the Pb emission rate.4,5,6  Essentially, the rate
of Pb emission has been shown to be a linear function of the average vehic-
ular speed.  A plot of this relationship for the LACS data is shown in
Figure 28.  This relationship, coupled with the increase in average weekday
afternoon traffic speed noted in 1977, accounts for the rather dramatic
increase exhibited by the 4-hour (1500-1800 hours) cross-freeway difference
(C-A) in Pb concentrations for 1977 (see next section).
                                     36

-------
14.3







12.9





11.4






10.0






 8.6
 5.7






 4.3






 2.9







  1.4






 0.0
   I    I   I   I   I   I    I   I   I   I   I    I   I   I    I   I    i   !   I    I   I    I




024      6      8     10      12     14    16      18    20    22
                                        HOUR OF DAY
                     Figure 27.  Carbon monoxide by hour (freeway median).
                                           37

-------
     11
     10
      8
CO
  o>
  a
 3   6
 o
                  I       I        I       I       I        I
                10       20     30      40     50      60      70



                      AVERAGE TRAFFIC SPEED (mph)
          Figure 28. A(C-A) Pb concentrations vs. average traffic speed.

                    1500-1800 hours, September 1976.
                                 38

-------
POLLUTANT TRENDS (BACKGROUND AND FREEWAY CONTRIBUTIONS)

     The primary objective of the LACS is to observe the long term trends in
ambient air pollutant concentrations attributable to automobiles in order to
determine the impact of the catalytic converter.  As was discussed earlier,
estimations of trends are more accurate when meteorology can be eliminated
as a variable.  This is possible during the summer 1500-1800 hour intervals
because of the near perpendicular winds that exist almost 100% of the time.
Examination of summer 24-hour averages and data collected during the winter
are much less meaningful because of the substantial increase in frequency of
non-perpendicular winds.  The trend data in. this section are presented in a
bar-graph format with a dotted trend line to visually compare years.  Because
there is often great variability from month-to-month, however, a paired t-
test based on monthly means was utilized to determine whether each year-to-
year change was statistically significant.  The changes that are significant
at the 95% confidence level are designated with an "S" adjacent to the
appropriate dotted line segment.  Those not marked are differences which may
have been due to chance.  It should be noted that this t-test considers only
the six summer season monthly average data pairs, and hence is a very con-
servative test.

     The primary pollutant emission levels designed to be reduced by the
catalyst are those of carbon monoxide (CO) and total hydrocarbons.  Because
of the simplicity of monitoring CO in the field as compared to hydrocarbons,
only CO is monitored as a direct measure of catalyst performance.

     Figures 29 and 30 show the CO background and freeway contribution (Site
C-Site A) on both 24-hour and 4-hour average bases.  Both graphs show
little change in the background CO concentration, although because of its
consistency during the 1500-1800 hour interval the slight increase from 1974
to 1975 was significant.  In the previous LACS summary report describing the
trends through 1976, the decrease in CO contribution in both the 24 and 4-
hour averages was attributed to substantial increased usage of catalyst
vehicles.  The apparent increase in the 1977 summer season CO contribution
does not test as statistically significant.  This perturbation could be a
result of the 10% increase in northbound traffic volume from 1976 to 1977.
The increase in CO contribution was also noted by Ledolter, et al,7 (Univer-
sity of Wisconsin) in applying predictive models to the LACS data.  Current
efforts examining the extended performance of the catalyst^ are indicating a
rapid decrease in catalyst efficiency in the first 20,000 miles.  This
coupled with reports of increased improper usage of leaded gasoline in
catalyst automobiles suggest that the CO ambient levels will probably not
decrease as rapidly as would be expected from the increased use of the
catalyst.

     The oxidation catalyst (the type installed since 1974) was not designed
to control the oxides of nitrogen, although the newer 3-way catalysts being
added to the 1979 and later model year vehicles should reduce NO  emissions.
The freeway contribution trends in NO levels as shown in Figuresx31 and 32
have shown apparent dramatic increases since NO monitoring began  in 1975.
These increases are much greater than the increases noted in traffic volume
and except for the 1500-1800 hour 1976 to 1977 period do not test as

                                     39

-------
a.

 •t
0)
•a

"x

§
o
10



 9



 8



 7



 6



 5
§   4
•s
3   3
          Simmer

           1974
                 Summer

                  1975
   Summer = April thru September
                                     Site A
Site C -  Site A
J
-95th Percentile


-Arithmetic Mean
               Figure 29.  LACS trend data. Carbon monoxide (CO) - all hours.
                                             40

-------
1U
9
8
E '
ft
. 6

-------
                                                        Summer
                                                         1978
                            Summer
                             1979
Summer = April thru September
Site
Site C -  Site A
                                                                          -95th Percentile

                                                                          -Arithmetic Mean
       Figure 31.  LACS trend data.  Nitric oxide (NO) - all hours.
                                            42

-------
a.
a.
ai
•o
o

u
.0
.45
.4
.35
.3
.25
.2
.15
.1
.05
0
^,
Of'"'
—
—
-
-
-
-
1 1 —
Summer Sum
1974 19
_i



* *
••^^
mer
75




Sumi
19
F"





ner
76





. .1 . MM
m^m
















i i i i
Suimrer Summer Summer
1977 1978 1979
 Summer = April thru September
Site A
Site  C - Site A
                                                                            -Arithmetic Mean
              Figure 32.  LACS trend data. Nitric oxide (NO) - 1500-1800 hours.
                                            43

-------
statistically significant.  These trends are probably real but, because of
the variability in the NO data (note the 95th percentile bars), are not
noted as such by the conservative t-test.  The background levels of NO
appear to show a slight increase on a 24-hour basis but none of the interval
changes are statistically significant.

     The nitrogen dioxide (NO,) background trends in Figures 33 and 34 show
no significant changes from 1974 through 1977.  The freeway contribution,
however, indicates the same increase pattern as NO and shows statistical
significance in 3 of the 4 yearly intervals.  Since the background ozone
levels (Figures 35 and 36) have remained relatively constant, the rate of
conversion of NO to N02 should show corresponding increases.

     Catalyst equipped vehicles have lower emission rates of aerosols than
those without catalysts because of particle decomposition at the elevated
temperatures and because of the exclusion of Pb from the fuel.  Therefore
the total suspended particulate (TSP) trend levels should also be indicative
of catalyst performance.  The background levels of TSP in Figures 37 and 38
show no significant changes.  The freeway contributions, however, showed
significant decreases from 1975 to 1976 (probably due to the catalyst), but
from 1500-1800 hours showed a significant increase from 1976 to 1977.  The
4-hour membrane data (Figure 39) show the same trend.  This increase is
partially due to the increased traffic speed resulting in a larger portion
of resuspended particles.  The decline of the 24-hour trend for the same
period did not test as significant because of a high degree of month-to-
month variability during the summer of 1977.

     The rise in usage of unleaded fuel in catalyst vehicles was expected to
result in lower ambient Pb as catalyst usage increased.  As was pointed out
earlier, however, contrary to CO, Pb emissions apparently increase rapidly
with increased average speed.  Adding the 5th lane northbound to the freeway
changed the driving patterns substantially, resulting in the increases noted
in Figures 40, 41, and 42.  It is reasonable to conclude that the decrease
from 1975 to 1976 is a direct result of unleaded fuel usage, since traffic
and meteorological parameters were not significantly different during those
years.  The increase in average speed from 1976 to 1977 resulted in trend
levels that must be corrected for traffic flow effects before comparison.
As was indicated in Figure 28, Pb contribution from the freeway is strongly
speed dependent.  The average weekday speed northbound in the 1500-1800 hour
period increased from 25 to 45 mph.  This would result in an increase of
freeway Pb contribution of 4 yg/m .  In addition, the increased speed prob-
ably causes a significant increase in turbulence intensity, resulting in a
larger concentration of reintrained large particle Pb.  The contribution of
these larger particles, however, is nearly impossible to quantify.  A more
definitive procedure for normalizing freeway contributions with both meteoro-
logy and traffic flow is currently being studied.

     The pollutant of primary interest early in the study was sulfuric acid
aerosol emitted from catalysts as a result of sulfur oxidation.   This aerosol,
it has been determined,   is quickly neutralized by ambient.ammonia (NH,) to
form ammonium sulfate.  Monitoring of the total sulfate (SOT) freeway contri-
bution has shown only small freeway contributions as shown in Figures 43, 44,
                                     44

-------
                                             Summer
                                              1977
                Summer
                 1978
              Summer
               1979
Summer  = April thru Septenber
Site A
Site C -  Site A
-95th Percentile

-Arithmetic Mean
            Figure 33.   LACS trend data. Nitrogen dioxide (NC^)  all hours.
                                           45

-------
£
IX

-------
,.111
                                            0.19
   Q.

   O.
    0).
    c
    o
.05
.04
.03
.02
.01
0
.01
.02
.03
.04
.05

-
1 P


II 1 1 1
1 1 1 1




T
|
mmmm
Summer Summer Summer
1974 1975 1976

Cj
I
i i
i

n

i i i i i
i i i i i
Summer Summer Summer
1977 1978 1979
Sjmmer  = April thru September
            Site A
Site C  - Site A
-95th Percent! le


-Arithmetic Mean
                      Figure 35.  LACS trend data. Ozone (03) - all hours.
                                              47

-------
o
3
    -.01
   I      I      I     I     I      I      I      I      I     I     I

Sunnier      Summer      Summer       Summer      Summer      Summer

 1974        1975        1976         1977        1978        1979
    Summer = April  thru September
                               Site A
Site C -  Site A  |—i  - Arithmetic Heart
                                                             n
                   Figure 36   LACS trend data. Ozone (03)~- 1500-1800 hours.
                                              48

-------
   200


   180


   160

   140


"E 120
•—
 CTl
 7 100
a-
£
    30=


    60

    40

    20

     0
                                I      I      I
           Summer
            1974
Summer
 1975
Summer
 1976
Summer
 1977
Summer
 1978
Summer
 1979
  Summer = April thru September
                   Site A
                      Site C - Site A
                                -95th Percent!le

                                -Arithmetic Mean
                  Figure 37.   LACS trend data.  TSP (Hi-Vol)  0-23 hr. average.
                                            49

-------
         Summer
           1974
Summer
 1975
Summer
 1976
Summer
 1977
Summer
 1978
Summer
 1979
Summer = April thru September
                   Site
                      Site C - Site A
                                                                          -95th Percentile

                                                                          -Arithmetic Mean
               Figure 38.   LACS trend data. TSP (Hi-Vol) - 1500-1800 hours.
                                          50

-------
        Summer
         1974
Summer
 1975
Summer
 1976
Summer
 1977
Summer  = April thru September
                   Site A
Summer       Summer
 1978         1979
                     Site C - Site A
                               -95th  Percent!le

                               -Arithmetic Mean
            Figure 39.   LACS trend data.  TSP( Membrane) - 1500-1800 hours.
                                         51

-------
 20


 18


 16

 14


 12


 10

   8


   6

   4


   2

   0
        Summer
          1974
Summer
 1975
Simmer
 1976
Summer
 1977
Summer
 1978
Summer
 1979
Summer = April thru September
                   Site A
                     Site C - Site A
                                                                           -95th Percent!le

                                                                           -Arithmetic Mean
               Figure 40.  LACS trend data.  Lead (Hi-Vol} - 0-23 hr. average.
                                          52

-------
4— v>
IS
16
14
E 12
^^ ,
^*»*
CD
: 10
T3
* 8
6
4
2
0
MHO*
MHVh
•HUB
•••


-
-
1 L esa

mm
JU<



•• (D


1 EH999
•




«v

—
.^
•I




T
n








•








1 1 1 1
Summer Summer Summer Sunnier Summer Summer
1974 1975 1976 1977 1978 1979
Summer  = April thru  September
Site A
Site C  - Site A
-95th  Percentile




-Arithmetic Mean
               Figure 41.  LACS trend data. Lead (Hi-Vol)  1500-1800 hours.
                                           53

-------
16
16
14
= 12
*%.
TI
; 10
a
u
J 3
6
4
2
n
-
-
-
—
-
-
-


•
mm
mm
m






-J~


•
' i tm

(§>••''
*







(D •
i












i i i i
Summer Summer Sunmer Sunmer Surnner Summer
1974 1975 1976 1977 1978 1979
Summer = April  thru September
Site A
Site C  - Site A
-95th  Percentile




-Arithmetic Mean
            Figure 42.  LACS trend data.  Lead (Membrane)  1500-1800 hours.
                                        54

-------
en
3.
cu
4->
03
3
00
           Summer
            1974
Summer
 1975
Summer
 1976
Summer
 1977
Summer
 1978
Summer
 1979
 Summer = April  thru September
                   Site A
                       Site C - Site A
                               -95th Percenti le

                              i-Arithmetic Mean
           Figure 43.  LACS trend data. Sulfate (Hi-Vol) - 0-23 hr. average.
                                             55

-------
                   33.8
       30.6  I      27.4   I
 I            .            v
              I      I      I      I     I      I
            Sunnier
             1974
Summer      Summer
 1975        1976
Summer
 1977
Summer =  April thru September
                 Site A
Summer      Summer
 1978        1979
           Site C - Site A
                   -95th Percentile

                   -Arithmetic  Mean
        Figure 44.   LACS trend data. Suifate (Hi-Vol)-1500-1800 hours.
                                               56

-------
and 45.  The 4-hour hi-vol data is considered suspect because of artifact
sulfate formation.  The 1500-1800 hour membrane contribution in the summer
of 1977 was only 1.2 yg/m , compared to a background of 11.1 yg/m  .  The
slight increases in freeway sulfate contribution though not significant may
be related to the increased average speed and total traffic volumes.  Ammonium
and nitrate ions have been monitored at the LACS (Figures 46 and 47) but
cross-freeway differences do not appear to be significant.

     The background and freeway contribution of SO? on a 24-hour basis shown
in Figure 48 showed significant increases from 1975 to 1977.  The absolute
magnitudes of these values are very small, both being less than 0.01 ppm.

     A summary of the pollutant trend significance tests appears in Table 1
(on page 85). The overall conclusions obtained from the LACS trend data to date
suggest that while the previous reports used the pollutant data to discern
trends without making corrections for meteorology or traffic parameters, this
simplistic approach isn't sufficient to compare data sets before and after
the significant changes in traffic flow caused by the addition of the lane
northbound in early 1977.  It also is probable that downwind Site C is much
more strongly influenced by the nearer northbound lanes than the southbound
lanes.  A concerted effort to apply normalizing7factors (such as the vector
components used by the University of Wisconsin)  will be made in future
reports in order  to more accurately analyze data trends.  These normalized
data should  then  be related to actual on-roadway exposure by developing in-
roadway/roadside  concentration relationships based on the CO monitoring at
Site F (center of the freeway).  If possible this exposure effort should
also examine an aerosol constituent such as Pb to determine if the higher
in-roadway levels of gases are indicative of higher aerosol levels.


LINEAR COMPARISONS

     Selected aerosol measurements at the LACS are made by more than one
method to provide confirmatory and method comparison information.  These
simultaneous measurements allow methods to be compared under near-background
conditions (Sites A and B) and at sites strongly influenced by the freeway
(Sites  C and D).  Because of the very large data base coupled with the
extensive quality control measures, meaningful correlations can be made that
demonstrate  long  term field performance.

     The high volume (hi-vol) sampler has been the primary aerosol measure-
ment method  used  at the LACS.  But because of the reactive nature of the
glass  fiber  filter, the sulfate values were determined to be parstly artifact.
The low volume membrane sampler, 0.14 m /min. compared to 1.4 m /min. for
the hi-vol sampler, has been operated,utilizing relatively inert cellulose
filters.  In the  previous LACS report  the hi-vol sampler was shown to be
more repeatable for mass than the membrane sampler for 4-hour samples in
side-by-side comparison testing (coefficient of variation of 5% compared to
15%).  The results of nearly 500 data pairs comparing 4-hour hi-vol and
membrane samples at Sites A and C are shown in Figures 49 and 50.  Each data
point  indicates a single pair of values.  A number instead of a data point
indicates multiple points of the same value.  It is apparent that there is

                                     57

-------
                  27.9
      22.9
       22.2

ID
    20

    18 -

    16

    14

    12

    10
      4


      2

      0

     -2

     -4
           Summer
            1974
Summer
 1975
Summer
 1976
Summer
 1977
Summer
 1978
Summer  = April thru September
                Site A
Summer
 1979
                      Site  C  - Site A
                              -95th  Percentile

                             i-Arithmetic Mean
       Figure 45.  LACS trend data. Sulfate (Membrane)-1500-1800 hours.
                                           58

-------
E

Dl
C
O
    Summer = April  thru September
-95th  Percent!le

-Arithmetic Mean
              Figure 46.   LACS trend data.  Ammonium (Hi-Vol) - 0-23 hr. average.
                                            59

-------
         Summer
          1974
Summer
 1975
Summer
 1976
Summer
 1977
Summer
 1978
Summer
 1979
Summer =  April thru September
                   Site A
                      Site C - Site A
                         L
                   -95th  Percent!le


                    Arithmetic Mean
             Figure 47.  LACS trend data. Nitrate (Hi-Vol) - 0-23 hr.  average.
                                          60

-------
    50

    45

    40

•^  35
 en
 t  30
 01
 TO

 125
 t  20
 M-
 5  15

    10

     5
                                                              I
                                                  I
           Summer
            1974
Summer
 1975
Summer
 1976
Summer
 1977
Summer       Summer
 1978         1979
  Summer = April  thru September
                  Site A
                     Site C - Site A
                                                                              -95th Percent!le

                                                                              -Arithmetic Mean
             Figure 48.  LACS trend data. Sulfur dioxide (S02) - 0-23 hr. average.
                                              61

-------
                      TABLE I
Summary of Pollutant Trend Significance Tests
0: No Significan Change
+: Significant Increase
-: Significant Decrease

Pollutant
CO



NO



NO-
L.


o_
•*


TSP





Pb





so4
T




NH4

N03

so?

Data Base
All Hours

1500-1800 Hrs

All Hours

1500-1800 Hrs

All Hours

1500-1800 Hrs

All Hours

1500-1800 Hrs

0-23 Hi Vol

15-18 Hi Vol

15-18 Membrane

0-23 Hi Vol

15-18 Hi Vol

15-18 Membrane

0-23 Hi Vol

15-18 Hi Vol

15-18 Membrane

0-23 Hi Vol

0-23 Hi Vol

0-23 Bubbler


A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
Trend/Period
74-75 75-76 76-77 Overall*
0000
0-00
+ 000
+ -00
00 +
000
000
0 + +
000
+ 0 +
000
+ + +
0
0
0
0
0000
0 - 0 -
000
+ 0
000-
0 - + 0
0000
o-oo
000
- + +
0 - -
0 + +
o-oo
+
0 0
0
0 0
000
0 0
000
000 +
0 0
0 - + o
0 0 + n
*Uverall: /4-// or /b-//
                        62

-------
    400-
     350-
                                                               n = 490
                                                               r = .378
                                                               Y = 46.0161 + .4082 X
                                                               1 :  Intercept?'0 with 95% Confidence
                                                              - 2 :  Sloped 1 with 95% Confidence
     300-
co
     250-
 Q.
 {2
 01
 S
 HI
200-
     150-
                       	*_f *.	*	•_
                        •   ••     "    •*
                       	v	t.».»__«.	2	
                         * * • *•  2  *•
          	*	„	2,	» ._.?•••	•
     100-
      50-
                    50
                           I
                          100
150        200        250

    Hi-VolTSPfcg/m3)
                                                                            300
350
400
                 Figure 49.  Membrane TSP vs. Hi-Vol TSP.      Site A: 1500-1800 hours.
                                                  63

-------
n
500>



450-



400-



350-



300-



250-
 QC

 §  200-
    150-
    100-
     50-
                                                              n = 494
                                                              r = .462
                                                              Y= 30.71 i
                                                              1 :  Intercept^ 0 with 95% Confidence
                                                              2 :  Sloped 1 with 95% Confidence
                       •• • **2 2  2* • •*
                50
                     100
150
200
       250     300

Hi-Vol TSPO/g/tn3)
350
400
 I
450
500
                 Figure 50.  Membrane TSP vs. Hi-Vol TSP.      Site C: 1500-1800 hours.

-------
very poor correlation between  these  samplers when  used on a 4-hour-basis.
The slopes and intercepts suggest  that at very  low levels (<75yg/m  ) the
membrane sampler produces higher values  than the hi-vol, and the converse at
higher levels.  The reason for the poor  correlation between these two samplers
is apparently related to the small size  of collected sample, since  the
correlation improves significantly in the 24-hour  measurements shown in
Figures 51 and 52.  These^wo  plots  show much stronger correlations and far
less scatter.  Lee, et al   in a similar comparison study in England generated
a regression equation of y=18.134+0.772X, which compares very well with the
data from Site B.  The correlation coefficient obtained by Lee of 0.922 (666
data pairs) for 24-hour sampling,  however, indicates better agreement than
that shown by the LACS data.   Recent aerosol collection efficiency testing
of the LACS hi-vol sampler and membrane  samplers has shown that the,hi-vol
sampler has the greater efficiency for particles greater than 20um.
Apparently there is a significant  concentration of large particles  (especi-
ally at Site C) which are more efficiently collected by the hi-vol sampler.

     The comparison of the Pb  analyses for the  same samplers are shown in
Figures 53, 54, 55 and 56.  Again  there  is a better correlation between the
samplers for measurements made over  24 hours (Sites B and D), but the scatter
about the regression lines is  substantially less than that observed for TSP.
This would indicate that the poor  agreement in  the mass measurements is due
primarily to factors related to analysis and sample handling.  Note that the
hi-vol Pb is determined by Atomic  Absorption (AA)  by Rockwell, whereas the
membrane Pb is measured by X-Ray Fluorescence (XRF) at Lawrence Berkeley
Laboratory (LBL).  Therefore,  these  methods comparisons are composites of
sampling and analysis variables.   Overall the comparison between these
methods is very good, especially on  a 24-hour basis.  It appears that mem-
brane sampling with XRF analyses would be a viable candidate as an  equivalent
method to the proposed hi-vol  Pb method.

     The membrane sampler was  added  at the beginning of the study to confirm
(on a different sampling substrate)  the  freeway contribution of sulfates.
It has been shown that there is only a small freeway contribution of sulfate
and that, especially on | short term 4-hour basis, there is a significant
artifact formation of SO..  As can be seen from comparing Figures 57 and 58,
which were samples averaged over 4 hours, with  Figures 59 and 60  (24-hours),
the length of collection time  has  a  great influence over correlation, bias,
and data scatter.  The 24-hour plots indicate that a hi-vgl operated for
this time interval has no more than  1 yg/m  additional SO^ than a membrane
sampler using a cellulose ester filter.
     The comparisons of  SO/, measurements  just  described  involved  the  same
 analysis technique  (methylthymol  blue)  but  different  samplers.  The membrane
 filters are also analyzed by  XRF  for  total  elemental  sulfur.   If  these
 latter measurements are  plotted against one another for  the  same  sample, a
 determination can be made of  the  fraction of the  total aerosol  sulfur associ-
 ated with water soluble  sulfates.  As can be seen from Figures  61, 62,  63,
 and 64, there is little  difference in the degree  of scatter  or  strength of
 correlation between the  4-hour and the  24-hour measurements.   This would
 suggest that the analytical methods are adequately sensitive for  the  amount
 of material collected  in either time  interval.  The stoichiometric ratio of

                                      65

-------
   350—
   300-
                                              n = 237
                                              r = -622
                                              Y= 16.5511 +.713^ X
                                              1 :  Intercept $ 0 with 95% Confidence
                                              2 :  Slope 1 1 with 95% Confidence
   250-
ro
 at
 85 200-
 iu
 z
 oc
 § 150-
 01
 5
   100-
    50-
                                           1	1	
                                           150         200

                                            Hi - Vol TSP (M9/m3)
50
100
                                                250
                                                 300
                                                                         350
                 Figure 51.   Membrane TSP vs. Hi-Vol TSP.     Site B: 0-2300 hours.
                                                66

-------
   250-
   200-
.E
Ol
.5
o.
= 150-
LLJ

<
QC
<£.
iu  100-
    50-
                                                                Intercept ^ 0 with 95% Confidence
                                                                Slope ^ 1 with 95% Confidence
                                        100              150

                                          Hi - Vo\ TSP (/jg/m3)
                                                                        200
250
                Figure 52.  Membrane TSP vs. Hi-Vol TSP.     Site D: 0-2300 hours.
                                              67

-------
00
                       11-
                      10-
                       9-
                       8-
                    —«•  "J mm

                       6-
                    <  5-
                    tt  °
                    GO

                    LU
                    S  4-
                       2-
                                         I
                                         2
                                                                                          ^^^	 ^
                                                                         ~z
                                                                            z_
                                                                                  J
                                                                                 n = 334
                                                                                 r = .929
                                                                                 Y= .0911 + .994 X
                                                                                 1 :  Intercept # 0 with 95% Confidence
   I
   5

Hi - Vol Pb
I
8
I
9
10
                                                                                                                11
                                   Figure 53.   Membrane Pb vs. Hi-Vol Pb.     Site A: 1500-1800 hours.

-------
                                         	  1  : Intercept ^ 0 with 95% Confidence
Figure54.  Membrane Pb vs. Hi-Vol Pb.     Site C: 1500-1800 hours.

-------
   14-
   12-
   10-
E

J   8-

Q_
til
S   6-
ui
    4-
    2-
                                                             z
                                                                -i—L  _*
                             7_
    TX77
                                      X" :/
                n =  127
                r =  .911
                Y =  .428  + 1.022  X
                            I
                            4
 6          8

Hi - Vol Pb (/ig/m3)
                                                             10
I
12
14
                Figure 55.  Membrane Pb vs. Hi-Vol Pb.     Site B: 0-2300 hours.
                                         70

-------
   12-
                                                            __. n = 125
                                                            _ r = .867

                                                              Y= ,322  +1.061  X
   10-
    8-
I
.O
Q.

LLJ   6-


<
CC
OQ


LJJ
                                            .    •
    4-
    2- -
                                    I
                                    4
10
12
                                           Hi - Vol Pb
                  Figure 56.  Membrane Pb vs. Hi-Vol Pb.     Site D: 0-2300 hours.
                                              71

-------
                       50-
                       40-
ro
                   n
                    i
C/I
LU

<
cc
CO
5
01
    30-
                       20—
                       10-
                                                                                    n  =  493
                                                                                    r  =  .834
                                                                                    Y=  -1.1801 +.779ZX

                                                                                    1  :  Intercept^ 0 with 95% Confidence
                                                                                    2  :  Sloped 1 with 95% Confidence
                                            I
                                            10
                                          I
                                          20
30
40
                                                                                                                   50
                                                               Hi - Vol S04 (M9/m3)


                                  Figure 57.   Membrane S04 vs. Hi-Vol S04.      Site A:  1500-1800 hours.

-------
     50-
     40-
                                                                   n = 498
                                                                   r = .804
                                                                   Y = -2.4951 + .8022 X
                                                                   1 :  Intercept/0 with 95% Confidence
                                                                   2 :  Sloped 1 with 95% Confidence
CO
 -I   30-
 Ul
                                                                   ~
 cc
 CD
 ^   20-
     10-
                          10
20
30
 I
40
                                                      50
                                             Hi - Vol S04 (pg/m3
              Figure 58.  Membrane S04 vs. Hi-Vol S04.       Site C: 1500-1800 hours.

-------
   40-
   30-
                                                                  z
                                                                      z
.E
O>
m   20-
QQ
s
    10-
                             «>•—*~
                                                     	n = 209
                                                     	r = .960
                                                            Y = -.987' + .996  X   	
                                                            1 : Intercept f 0 with 95% Confidence
                                         Hi - Vol S04 (ng/m3)


                Figure 59.  Membrane SO4 vs. Hi-VOI S04.      Site B: 0-2300 hours.
                                            74

-------
en
                   .E

                   O)
                   01

                   <
                   
-------
    50-
                                                             n = 443
                                                             r = .930
    40-
                                                             Y = .2181 + .3222 X
                                                             1 :  Intercept^ 0 with 95% Confidence
                                                             2 :  Slope ^ 1 with 95% Confidence
to
 £
 ro
 3.
 V)
 cc
 CO
30-
    20-
    10-
                        i
                        10
                                     i
                                    20
30
40
50
                                        MEMBRANE SO4
               Figure 61.  Membrane S vs. Membrane 504.      Site A: 1500-1800 hours.

-------
   50-
                                                             n = 450

                                                             r = .915

                                                             Y= .3261 + .3202X

                                                             1 :  Intercept # 0 with 95% Confidence

                                                             2 :  Slope 1 1 with 95% Confidence
    40-
E   30--
O>
a.
V)

UJ
cc
CQ
5
UJ
    20- .
    10-
                       T
                        10
                           nr
                            20
~T
 30
40
50
                            MEMBRANE S04




Figure 62.  Membrane S vs. Membrane S04.
                                                           Site C: 1500-1800 hours.
                                              77

-------
    40-
                                                        _n = 136
                                                        _r = .922
                                                         Y = .592' + .2532 X
                                                        ~ 1 : Intercept ^ 0 with 95% Confidence
                                                        ~ 2 : Slope + 1 with 95% Confidence
    30-  -
ro
    20-
 cc
 m
    10-
                           10
 I
20
                                      MEMBRANE SO4 (ng/m3)


                 Figure 63.  Membrane S vs. Membrane SO^
 I
30
               Site B: 0-2300 hours.
                                                                                         40
                                            78

-------
   35-
   30 —
   25 —
   20-
       n =  138
       r =  .941
       Y =  .469' + .262Z X
       1 :  Intercept ^ 0 with 95% Confidence
       2 :  Slope ^ 1 with 95% Confidence
3:
CO
LU
cc
S  15-^
   10 —
    5-
                                10
                                             15
20
25
30
                                                                                                 35
                                          MEMBRANE SO4 (jug/m3)


                 Figure 64.  Membrane S vs. Membrane SO4.      Site D: 0-2300 hours.

-------
sulfur to sulfate on a mass basis should be 1/3 (0.333) if all of the sulfur
were in the form of sulfate.  The slopes of the Sites A and C data  (1500-
1800 hours) are almost exactly this, whereas the results for 24-hour data at
the other sites is significantly less than 0.333.  The analyst at LBL,
Mr. Robert Giaugue, noted that the difference between the data sets was not
caused primarily by sulfur in a form other than sulfate, but a sampling
problem that primarily affects XRF measurements.  Apparently the 24-hour
samples during the high humidity early morning hours.cause moisture to
appear on the filters which dissolves some of the S0« and soaks it  into the
filter.  Since XRF is a surface measurement technique, this portion of the
sulfur is not measured.  If penetration into the filter is prevented, the
XRF sulfur values give an extremely good estimation of the total sulfate
present.

     The final set of plots in Figures 65, 66, 67 and 68 show the comparison
of lead (Pb) with bromine(Br) at the four LACS sites.  Lead in gasoline is
primarily present in the form of PbBrCl, such that freshly generated auto
exhaust should contain a stoichiometric ratio of Pb/Br of 2.59.  It has been
shown   that bromine is lost rapidly from the aerosol as it ages.  Therefore
the ratio of Pb/Br increases as the particles are transported from the
source.  The background measurements at Site A are not affected by the
freeway emissions during the 1500-1800 hour interval.  Therefore these Pb/Br
ratios should be higher than those at Site C.  Examination of the slopes at
Sites A, B, C and D indicate the freeway influence and the effect of diluting
the fresh aerosols with the background aged aerosols.  The very high corre-
lation coefficients are evidence that almost all of the Pb observed at the
LACS sites are probably automobile generated.
                                     80

-------
CO
    14-
    12-
    10-
     8-
                                                      n = 263
                                                      r = .965
                                                      Y = .4321 + 2.44S2 X
                                                      1 :  Intercept/0 with 95% Confidence
                                                      2 :  Slope / 1 with 95% Confidence
                          z
 Q.
 LU
 Z
 EC   _
 m   6"

 LJJ
     4—
      2 —
              z
	/
                                              6           8

                                           MEMBRANE Br (ug/
                                                            10
              Figure65.  Membrane Pb vs. Membrane Br.     Site A: 1500-1800 hours.
                                               81

-------
00
ro
o>

£
UJ
<
cc
ffl
UJ
5
                                                                                    n = 462
                                                                                    , = .950
                                                                                    Y= 2.2451 + 1.8182X
                                                                                    1 : Intercept^ 0 with 95% Confidence
                                                                                    2 : Sloped 1 with 95% Confidence
                        4-
                                                              MEMBRANE Br fog/m3)
                                 Figure 66.  Membrane Pb vs. Membrane Br.
                                                            SiteC:  1500-1800 hours.

-------
00
CO
                                                                                  n = 140
                                                                                  r = .957
                                                                                  Y = 1.0791 +2.1902 X
                                                                                  1 :  Intercept ^ 0 with 95% Confidence
                                                                                  2 :  Slope i-1 with 95% Confidence
                                                              MEMBRANE Br (Mg/m3)


                                  Figure 67.  Membrane Pb vs. Membrane Br.      Site B: 0-2300 hours.

-------
    12-
    10-
                                           n  =  140
                                           r  =  .796 ,       _
                                           Y=  1.2011+2.0452  X
                                           1  :  Intercept 7s 0 with 95% Confidence
                                           2  :  Slope # 1 with 95% Confidence
                                   7_
                                 ~7
     8-
to
                            z
 a.
 uj   6-
 X.
 m

 UJ
                 -fs	yt« «
                  »   •««•
2 «
2«
                                                                    I
                                                                    8
                                                            10
12
                                           MEMBRANE Br (ng/m3)


                  Figure 68.  Membrane Pb vs. Membrane Br.      Site D: 0-2300 hours.
                                                84

-------
Table 1:   SUMMARY OF POLLUTANT TREND SIGNIFICANCE TESTS

0:  NO SIGNIFICANT CHANGE
+ :  SIGNIFICANT INCREASE
-:  SIGNIFICANT DECREASE
•
POLLUTANT
CO



NO



NO2



03



TSP





Pb





S04





NH4
N03
SO2
DATABASE ,
ALL HOURS

1500-1 800 Hrs

ALL HOURS

1500-1 800 Hrs

ALL HOURS

1500-1 800 Hrs

ALL HOURS

1500-1 800 Hrs

0 -23 HI VOL

15-18 HI VOL

15-18 MEMBRANE

0 -23 HI VOL

15-18 HI VOL

15-18 MEMBRANE

0 -23 HI VOL

15-18 HI VOL

15-18 MEMBRANE

0 -23 HI VOL
0 -23 HI VOL
0 -23 BUBBLER
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
A
C-A
TREND/PERIOD
74-75
0
0
+
+












0
0


0
0
0
0




0
—





0
0
0
0
75-76
0
—
0
_
0
0
0
0
0
+
0
+




0
—
0
—
0
—
0
—
0
—
0
0
-
+
—
—
—
0
0
0
0
0
76-77
0
0
0
0
0
0
0
+
0
0
0
+
0
0
0
0
0
0
0
+
0
+
0
0
0
+
-
+
0
—
0
0
0
0
0
0
0
+
OVERALL*
0
0
0
0
+
0
0
+
0
+
0
+

0


0
—
0
0
—
0
0
0
0
+
-
+
0
—
0
—
0
0
0
0
+
0
0
'OVERALL: 74-77 OR 75-77
                            85

-------
                                 REFERENCES

1.    The Los Angeles Catalyst Study Symposium.  EPA-600/4-77-034, June
     1977, U. S. Environmental Protection Agency, Research Triangle Park,
     North Carolina  27711.
2.    Storage and Retrieval of Aerometric Data (SAROAD) Parameter Coding
     Manual.  APTD-0633, July 1971, U.S. Environmental Protection Agency,
     Research Triangle Park, North Carolina  27711.

3.    Quality Assurance Handbook for Air Pollution Measurement Systems.
     EPA-600/4-77-027, May 1975, U.S. Environmental Protection Agency,
     Research Triangle Park, North Carolina  27711.

4.    "Particulate Lead Components in Automobile Exhaust Gas," D.A. Hirschler
     et. al., Industrial and Engineering Chemistry July 1957.

5.    "Atmospheric Lead:  Its Relationship to Traffic Volume and Proximity
     to Highways," R.N. Daines et. al, Environmental Science and Technology,
     April 1970.
6.    "Measurements of Particulate Lead on the M4 Motorway at Horlington,"
     M.G. Bevan et. al, Great Britain Department of the Environment, 1974.

7.    Statistical Analysis of the Los Angeles Catalyst Study Data.  Johannes
     Ledolter, George C. Tiao, Spencer B. Graves, Jian-tu Hsieh, and
     Greagory B. Hudak, University of Wisconsin Statistics Department, final
     report for EPA contract 68-02-2261, August 1978.

8.    Characterization of Sulfate and Gaseous Emissions from California
     Consumer-Owned Catalyst Equipped~Vehicles.  R.J. Herling, R.D. Gafford,
     R.R. Carlson and A. Lyles, Olson Laboratories, final report on EPA
     contract 68-02-2232, 1977.

9.    Private communication.  Robert D. Giaugue, Lawrence Berkeley Laboratory,
     July 26, 1978, to Charles E. Rodes, EPA/EMSL/RTP.

10.  "Bromine Loss from Automotive Particulate Associated at California
     Sites."  R.A. Eldred, T.A. Cahill and R.G. Flocchini, University of
     California at Davis, presented at the 71st APCA meeting, June 25, 1978,
     Houston, Texas.

11.  "The Evaluation of Methods for Measuring Suspended Particulates in Air,"
     R.E. Lee, Jr., J.S. Caldwell and G.B. Morgan, Atmospheric Environment,
     Volume 6, pages 593-622, 1972.

12.  "Aerosol Characterization of Ambient Particulate Samplers Used in
     Environmental Monitoring Studies"
                                     86

-------
APPENDIX
   87

-------
                 DBS    COUNT     SPEED    DENSITY     TSP       PB~     CO       NO
CO
CO
1
2
3
q
5
6
7
6
9
*
10
I!
iz
13
!•»
15
,fc. . , ,. 	 .„
'16
508 17
1 uuo
ii67i ;
19953 " ""••'
51 107
51878 ! '
11352 "'f
*t

-------
O3
'
COUNT
COUNT 1*000000 -*
	 »0000'~ 	
-SPEED 	 ' - --r93Sr279-- ~\ .
• 0001
DENSITY '«90397<« °° »
• oOoi
TSP ~*Q7i\H7
.7889
PB «•« 856827 -t
-v ,
-CO— ' - .692257 ».
,0032
NO. -.375777 .
• - •• . 1 HBS
u
Sf>££.
9o527v
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98922H
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30088 ,v
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,OTJO.
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57773;
• D I 6 2
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OENSJTY
.903*7.,
» 0 0 0 t 	
oOOOl
1 .00.0000
.0000
-. 276H 1 3
» 3005
-.95260'''
• BCOTT-
•76H37I
.OOOfl
-.5198JB
.0372
t r * t . t 
T S P
-»0"/l i'tV

- «. 2 7 6 H i 3
• 3DCS
'0000
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".S56827 «69?257
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•OOOJ .oOOS
-,95?609 .76,37,
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• 5 8 36 '02^3
»»OOCOCO '».7Mt;^68
.DOOO ~ ".0012 ""
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               A-2

-------


CAI_ IF OR Hi A
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            SAMPLING INTERVAL-1-01  Hour Data

-------

Tt*R NUB

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LOS ANGELES
•
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50 60. TO


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67.0
75.0
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79.0
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70.0 82.0
79.0 88.0
77.0
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55.2
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8.68
9.31
9.27
10.47
10.49
6.48
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8.4F
9.60
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4.82
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54.53
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2.86
1.98
1.98
A-4  POLLUTANT-62101  Temperature
     METHOD-11 Instrumental Spot Reading
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     SAMPLING INTERVAL-1-01 HourData

-------
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1.61 |.2I 7.21
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1 .73 | .32 2.73
1,11 i .71 7.13
	 7.S1 	 '-.AA-- 7r93 —
1.31 .«2 2.13

1.10 3.14 1.99
? uc u.?5 I.A7
3.11 1.01 .81
* Tl i.A^ .A9
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3.31 j.52 .95
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7.91 |.11 2.68
7.9? I .9P ?.3
-------
iRiruurTir srOHrffiif

CALIFORNIA
LOS ANGELES
OSM1 60003AOS
-LOS ANGELES
OS1I80005A05


	
C -
c -
c -
c -
c -
c -
c -
YEAR NUM

OCT1-MARS 921
APR5-SEP5 3518
OCT5-MAR6 2873
OCT6-MAR7 3366
APR7-SEP7- 4123
OCT7-MAR8 3379
NOT1NRNGE 724

OCT1-MAR5 1200
APR5-SEPS. 3890
OCTS-MAR6 2736
- APR6-SEP6 -453*
OCT6-MAR7 3110
.APR7-SEP7— JJ22-X
OCT7-MARB 3316
NOT fNRNGE — «*»
OCT1-MAR5 88|
OCTS-MAR4 7594
APR4-SEP6- 3381
OCT4-MAR7 3272
APR7-SEP7-399J
OCT7-MAR8 3189
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190- .120- .070-
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230- .115- .OB5-
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.140 .220
,160 .216
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,151 .201
,167 .751

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,650 .760
.665 7.310
.610 .799
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.110
,^67
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,269
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,219
.252
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.117
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,1071
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.1971
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, 1478
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.1*17
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,777*
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MEAN STO

.09 7. SI
•11 2.57
,13 7.38
,11 7,37
,ni 7, AX

.72 ,90
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.19 .16
. 1 A .11
.70 .97
.>« .75
.20 .97
.05 3,95
,03 1.87
,0| 5.83
	 .42 	 2»AM_
.03 1.53
	 .-OS 	 1.07 —
A-7  POLLUTANT-42601 Nitric Oxide
     METHOD-14  Instrumental Chemiluminescence
     UIMITS-07 Parts Per Million
     SAMPLING INTERVAL-1-01  Hour Data

-------
YEAR HUM
CALIFORNIA
051180003A05 OCT1-MAR5 1*73
OCTS-MARA 2859
OCT6-MAR7 3<»2H
OCT7-MAR8 3223
	 NOTfNRNsE 	 7-25 	
LOS ANGELES
D51I80005A05 OCT1-(1AR5 15*8
APR5-SEP5 1g98
OCT5-MAR* 2791
OCT*-MAR7 3i46S
M!N 10 20 30 10

LD .Q15 .025 .Q35 .QlO
LO .010 »015 «02C »025
LO .020 -030 -010 .015
LD "OlO «810 '015 "OUS
LD >Q19 .032 *010 >015
— LD *0l0 "Ot"''- ~»OI'-~ • 025"-
LD -020 «031 '037 .Q13
— LD- 	 LO 	 »U t4* 	 «02 1 — »03 1 ~
LD «020 »025 «o30 «035
LO -030 »C35 .Q35 .010 '
LO «025 .030 «035 .015
LD .031 .038 .015 .Q52
APR 7 -5Cp7 12 75 .UID "U^b •u1** .pi/ «U3J-"
OCT7-HAR8 3398 LD '025 .'031 'C35 .Qll
	 	 NOTJNRNSE 	 729 	 iOJ-1 	 »028 	 .Wl 	 T0-38- 	 c012~
50

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•122
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•133
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.157
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• 210
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.185
• 1 30
.187
-. 13* -
'200
• 101 -
.210
• 110
•210
• 198 —
.213
-•-20*—
.228
•HI-
MAX

.355
.280
.335
.351
.270
• 210
.310
.280
.321
.338
• 1 *7
An | i ni*L 1 1 1
MEAN STD

.051 .0110
.05* .0317
*035 «02"0
.058 .0358
.059 .0383
— i038 	 402*0—
.053 .0105
	 «053 	 r02*0 •-
.0*3 .0122
.070 .0122
• 0*9 -- 10373 —
.0*3 .0118
	 r052 •-- .0750
MEAN STO

.01 l'»7
--•03 -|»9t —
•05 1.77
•03 1 •'>
.05 1.77
n \ 1 M. fl U
•OS 1.82

— .05 — i «&9 -
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en
C - «
C '
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C -
C -
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OCT1-MAR5 M07
OCT5-MAR* 25*8
	 APR6-SEP*— 3312
OCTA-MAR7 3383
OCT7-MAR8 3Q92
NOTINHNtt 7111
•110- '025- «020- »OI5- -OIO- «005- «000
• 1*5- -020" *C|5- • 0 1 0 * "000 "PIS' »p?5
.225- '025- -020- '015- -010- .005- «000
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• 119
• 113
•1 |5
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fj-30-
.205
.213
.223
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5.05
2.73
a. lit
— f-ri 6
               A-8 POLLUTANT-42602 Nitrogen Dioxide
                   METHOD -14 Instrumental  Chemiluminescence
                   UNITS-07 Parts Per Million
                   SAMPLING  INTERVAL-1-01 Hour Data

-------
VO

TEAK Nun niK~
CALIFORNIA 	 -- 	 -- 	 	 • —
LOS ANGELES
054180003*05 OCT5-HAR"«"177S 	 L"D~
APR6-SEP6 3112 LO
1 OCT6-BBR7 3464 LB "
APR7-SEP7 4206 LO
OCI7-HARS 3308 LD
NOTINRN6E 723 LO
LOS ANGELES
OS*HJUUU5*U5 OCT5-FIAR6 1*50 LO ~
	 	 APR6-SEP6 3309 10
APR7-SEP7 4317 LO
OCT7-BAR8 3300 LO
NOT1NRN6E 585 LD
-. .— -.— 	 — _ — ™__--. -_ -gyu-i 	 A- f j j. 	 n'TVtF — ~
C - A APR6-SEP6 2928 .265-
C - A OCT6-KAR7 3359 .588-
C - A APR7-SEP7 4170 .317-
C - A OCT7-MAR8 3099 .1S5-
C r A NOTINRN6E 564 .123-

	 10 	

LD
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.255
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.214
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ARITHMETIC
MEAN STO

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.036 .0395
7027 .0513
.039 .0428
.021 .0315
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.010 .0098
.010 .0098
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.011- .0285
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CEOMETRIC
REAM STB

.01 2.81
.02 2.45
.01 3.41
.03 2.45
.01 2.97
.02 2.«3_.-

.01 2.22
.01 2.27
.01 2.26
.01 2.32
.01 2.20
.01 2.00

.00 4.22
.02- 2.79
.01- 4.33
.02- 2.66
.00 3.99
.01- 3.04
              A-9  POLLUTAISIT-44201  Ozone
                   METHOd-11 Instrumental Chem[luminescence
                   UNITS-07 Parts Per Million
                   SAMPLING INTERVAL-1-01 Hour Data

-------
YFAR HUM

C»L JFORNI A
LOS ANGELES
-05J.LBD003A.05-.AP-RH-SEPa 	 U.5. 	
OCT1-HAR5 139
APR5..SEP5 |AI
OCT5-MAR4 112
APRA-SEPA ]73
OCT4-MAR7 134
APR7-SEP7 |01
NOTINRN6E 2
LOS ANGELES
05*iflon,o5Ap5 APRM-^F.P"* ji-1
OCT1-MARS J13
OCT5-NAR4 118
OCT4-MAR7 J39
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NOTINRN6E 5
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              A-10   POLLUTANT-11101 Suspended Part.
                    METHOD-91 Hi-Vol Gravimetric
                    UNITS-01  UG/CU Meter (25 C)
                    SAMPLING INTERVAL-7-24 Hour Data

-------

rnrn 	 mi* —
CALIFORNIA 	 	 —
LOS ANGELES
T354180003A05 APR4-SEP4 T"
OCT4-HAR5 102
" " APR5-SEP5 173
OCT5-MAR6 122
APR6-STF6 	 173~~
OCT6-HAR7 138
" " •" APR7-SEP7 109
OCT7-HAR8 66
NOTINRNGE 4
LOS ANGELES
054180005A05 APR4-SEP4 3
	 ' OCT4~-MAR5' 4T
APR5-SEP5 172
OCT5-MARA 119
APR6-SEP6 172
OCT6-MAR7 147
APR7-SEP7 108
OCT7-HAR8 62
NOTINRNGE 5
t
C - A APR4-SEP4 3
C - OCT4-HAR5 47
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C - OCT5-HAR6 t18
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C - OCT6-MAR7 137
.... c_.. — APR7-SEP7 1CZ
C - OCT7-HAR8 58
C - NOTINRNGE 4

WIN 10

74 	 74 '
LD 34
8 ' *2
16 35
10 26
19 39
15 38
11 23
17 17
106 106
LD 75
58 100
32 82
29 80
43 77
LD 94
LD 60
72 72

101- 7

20

74
50
55
46
53
50
31
17
106
93
116
95
93
91
109
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220- 4 32
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62
63
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106
105
125
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102
102
117
103
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56
37
57
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40

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66
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116
132
112
111
129
115"
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40
34
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50

77
77
86
72
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120
128
137
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116
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135
130
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48
44
39
57
60

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80 90

"~39 39 39 •"•• "95
89 107 126 164
85 93
94 105
80 .87
99 113
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84 93
17 33
120 120
134 170
146 156
140 152
121 132
131 143
142 151
139 151
109 109

81 81
55 57
67~ "74
54 59
47 51
42 48
60 65
64 68
ion 113
120 166
100 117
129 145
105 	 123
104 123
33 36
120 126
191 222
168 188
168 197
142 160
T5~5 1T3"
159 184
167 196
109 150
~8T 31
63 74
80 91
68 78
57 64
53 63
71 83
71 89
76 92

«5 9* '"

95 95
196 220
127 180
231 268
126 162
157 183
f35 240
204 232
38 ""• 38
126 126
253 279
201 236
235 268
169 217
1S7 217
211 296
236 274
150 150

31 	 T1 	
109 133
102 114
87 97
73 88
70 107
T02" 	 t7T—
99 143
'"92 ""92 	
ARITHMETIC GEOfllTRIC
MAX

95
266
298
347
196
185
369
248
38
126
279
255
278
227
~221 	
623
303""
150

31 -
133
140
122
123
163
221
92
BEAN

69
90
80
95
73
91
83
77
26
,117
141
142
136
119
142
132
106

48
47
62
43
44
34
54
69
STD MEAN STD

28.3 64.20 T.4B
50.4 78.75 1.68
16.0 73.10 1.53
58.3 81.45 1.76
34.3 66.27 1.56
40.4 83.45 1.53 >
44.0 73.22 1.65
53.9 62.90 1.88
10.9 24.25 1.49
10.3 16.89 1.09
60.4 29.19 1.51
35.1 37.72 1.28
47.7 28.50 1.41
31.9 14.57 1.30
37.2 19.25 1.34
61.2 30.46 1.51
58.4 21.11 1.52
28.9 2.48 1.31
36.9 36.54 2loi
35.6 53.42 1.71
43.1 29.93 2.32
19.7 40.39 1.53
30.8 24.96 2.18
58. 4~4 1.95" "1.2T"
42.2 42.11 2.00
18.5 66.64 1.30
A-11   POLLUTANT-11101 Suspended Part.
      METHOD-91 Hi-Vol Gravimetric
      UN ITS-01  UG/CU Meter (25 C)
      SAMPLING INTERVAL-3-04 Hour Data

-------
                                                                          ARITHMETIC
                                                                                     6EOMETRIC

CALIFORNIA
LOS ANGELES
054180003AC5




LOS ANEELtr
054180005A05




.
C - A
C - A
C - A
	 t '-"» "
C - A
C - A
t - A
C - A
TtAR

OCT4-MAR5
"APR5-STPT-
OCT5-HAR6
"APR6-SEP6
OCT6-KAR7
APR7-SEP7
OCT7-HAR8
MOTlNRNTf
APR4-SEP4
OCT4-HAR5
APR5-SEP5
OCT5-MAR6
APR6-SEP6
OCT6-KAR7
APR7-SEP7
OCT7-BAR8
NOTINRN6E

"APR4-SEP4
OCT4-WAR5
APR5-SEP5"
OCT5-KAR6
APR6-SEF6
OCT6-BAR7
APR7-SEP7
OCT7-BAR8
NOTINRN6E
NUB

34
«TT
39
157"
120
165
65
E
12
42
61
41"
156
125 "
167
62
8

If
33
' 60~
38
144 '
115
-154
58
7
TFIN

29
LD
— ID
8
LD
LD
LD
LD"
24
LD
LD
LD
3
4
LD
• 36

- 95-.
"140-
P4-
156-
218-
" 60-"
26-
36 "
1 U

LD
"7T
35
23
28
6
12
"CD-
24
LO
75
42
4 9
51
39
36

95-
78-
3
16-
20-
42-
-"27
0
36
VO

64
LD
57
54
36
45
21
19
LD
138
10
101
79
59
74
71
55
40

14
0
14
6
6
21
36
" TO

36
73
58
... 51
58
30
32
LD
180
39
120
90
69
f>6
79
75
40

22
0
19
12
16
29
39
— nr

99
78
83
64
60
64
39
44
LD
180
100
130
102
88
99
89
85
50

67
12
39"
25
22
29
44
40
40
~ 	 30"

116
87
78
71
52
57
6
192
119
142
110
95
108
95
102
61

" 75
29
45
29
27
39
43
44
60

119
101
" 107
82
	 81"
82
59
68
7
218
137
152
119
105
1 31
103
115
123

' 93"
33
51 ~
37
32
46
53
51
44
70

120
125
93
93
102
69
75
84
219
162
164
130
118
146
113
125
150

1f6
44
57
43
39
58
T8~
57
54
80

125
15T"
122
107
124
81
92
84
224
180
178
155
128
169
124
144
150

76
63"
45
53
70
63
64
59
- "90-

166
170
150
143
126
173
97
121
91
228
227
187
181
151
189
139
181
157

129
173
"" 87
59
69
102
76"
83
59
95

166
197
178
199
144
207
109
169
93
228
264
218
225
181
234
150
191
169

129
180
121
82
85
114
119
64
99 "

286
291
191
334
190
233
120
174
93
294
552
304
279
227
262
168
271
169

150""
456
229
120
123
189
"92
146
64
MAX

286
291
193
334
212
276
138
203
93
294
552
601
279
326
315
294
49J
169

150
456
423
120
212
257
261
392
64
MEAN

125
89
96
91
75
88
52
62
35
189
125
147
118
98
119
97
109
98

70
44
51
29
28
33
49
50
48
STD MEAN STD

65.2 10.46 1.64
72.4 69.54 2.03
47.8 86.37 1.60
62.7 75.06 1.86
41.1 65.38 1.67
55.0 74.32 1.78 _
33.2 43.43 1.80
45.7 49.80 1.93
44.9 21.84 2.67
66.3 78.52 1.41
111.8 92.97 2.15
80.2 28.72 1.67
54.2 7.28 1.55
48.9 87.89 1.60
58.1 6.64 1.59
36.6 90.90 1.44
72.9 90.71 1.84
57.0 84.99 1.71

69.1 49.43 2.29
125.0 14.86 4.39
"69.2 "29.85" 2.79"
36.6 17.62 2.68
39.0 16.21 2.83
63.5 15.07 3.48
25.0 43.41 1.62
56.0 33.53 2.46
10.9 46.80 1.25
A-12  POLLUTANT-11101  Suspended Part.
      METHOD-92 Membrane Sampler Gravimetric
      UNITS-01 UG/CU Meter (25C)
      SAMPLING INTERVAL-3-04 Hour Data

-------
o
o
n
- c At i r ft mi i A
LOS ANGELES
OCTM-MARS
OCTS-MAR6
OCT6-MAR7
, A r* n 7 ~ *? F" n 7
NOTINRNQt
LOS ANGELES
fl5Hl80QQ^An5 APn*i— Tn4
OCT1-MAR5
ft e» r> r «- ** F o 1
OCT5-MAR6
OCT6-MAR7
NOTINRN6E
C ~ A APRM~^"EF^
C .- A OCTM-HAF5
C - OCTS-MAR6
r m APir/.-1-Tr fi
C - OCT6-MAR7
C - NOTJNRNGE



139
fr fr ™
1 12
>j a
136
I n 11
2
1 1 3
I 7*1
118
139
5
6 ?
127
100
1 57
133
2
HIM


LO
• • L P
.60
• 20
LO
_ i n
1 .80
}• nn
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9 * n n
1. 10
i n
5. SO
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S.50-
3*1 nn -r
2 * to*"
? • nn IT
3»DQ-
t . 7 «.»
3.80



2.00
*_
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2.8o
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t »fio
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3.20
3.2Q
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A .nn

2 • fin
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1 • 5n
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3.8Q
	 »0—


2.80
2*60
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3.60
i _ on
1.80
6 i SO
1.70
*• *in
M.10
Si n
5.80
S.50
3 , JLft
.10"
» t gin
.10
? t 70
• 20-
3.80
	 M 	 »0-


3.30 H*10
3.10 3.10
• 60 1 -r¥Q •
H.30 4. 80
—2-. 1-0- — 2-*-6Q—
1.80 1.8Q
7 j ?n 7 «9n
,5.20 5.70
4 an f Ur\
M.7Q 5.20
C. Ai-t i . nn
6,60 7.1Q
7 * 00 7 . 30
S.6Q -5»6Q
q tHQ fi T 1 0
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'u -in u . 0 n
.SO ttOO
7 „ on 3 • MO
.80 1*30
1 1 70 5 t *0
3.80 3.8Q
	 U 	 60 	 M-

— 2-rJS 	 2.70— -3.-30-
1.60 S.OO 5.50
3.8Q M.30 5.00
5.30 5.80 6.70
3 . Bn 1^ 1(1 J • fiQ
1 .80 1 .80 1 .80
e • tn s»^n ° * 20
6.10 7.00 7.10
"T • 7n fl • 1 n fla^O
5.40 6.30 6.90
7,70 8.00 8.60
7 . 60 7 • 90 8 . 30
6.30 6.30 6. SO
fi«90 6t^0- 7* 30
1.50 1.90 2.50
5 . 1Q 5 .80 6 .50
1.60 2.30 2.70
— 3.-90— M-MO — -5 .20
1.70 2.3Q 3.00
1.30 B • 20 ^ * ftO
3.80 3*80 3.80
. „

--3.70
6.10
- 3.5o
3. S0
9 .90
8.20
-9.lt)
7. MO
9 . 1 0
6*$0
R . 1 n
3« BO
— 7.-2O
3«3Q
- 6«10
3«8o
3.6o
.. . .90 . 9« 	 M 	 HAJt 	

1.60— 5 f 60- 7 -.50 - 9.2B 	
7.10 7.8o 9.60 13.90
1.90 5tMO 6.10 7t?0
6*60 7.1Q 8.30 8.30
~M*00 M.Sfi S . MO 7.20 	
8.20 8.90 9.8Q 11*20
-..M.60-. 5.30- 5.70 6. MO 	
3.50 3.50 3.5Q 3*50
)0*70 11*20 12*00 12*^0
9.20 10.00 12.60 11.70
9.80 10.30 14*00- lt*SO
8. MO 8.9Q 10.30 1 1 '50
9.60 10.20 11.60 U'60
	 9 , 20 	 9 ^8 0— 1 0*60-12*1 ft- 	
7. |0 7.10 7.10 7.10
O,T(? ».'o IDt'O 'l-ln
1.90 5,80 8.10 8.70
8.30 9.10 lO.ln I0t20
1.|0 5. 10 6. MQ 6. MO
7«10 7.10 9*10 17.60
5.30 4.7Q 8. 80 9.10
7. |n 8. tO 9.7Q 1 | .80
3*60 3. 6Q 3.6Q 3*60
ARITHMETIC
Mf«N SID

2«55 — 1.639
M*59 2«069
3, 12 4 .680
M»l2 1.737
2*37-^.282-
S'lS 2.200
2.95 1.351
2*65 | .202
8*21- J.893.
6*3M 2*391
7.7H l .439
5*77 2*0*1
i.cj 1.019
7*12 2.026
7*51 -4.613
6*20 *663
5.0* 2*1^3
1*65 2*36|
E 1.2,6 	 2.116..-
1*71 J.972
M*t6. 2*121
1*98 2*183
4*61 ?«J98
3*70 .111
GEOMETRIC
MflM STO

2. IS

».e0
2.02 J" 82 .
3*80
2. 09
5.05
2.69
2.11
e.ns
S.93
7.57
S.MS
f •?*
7. )6
7.37
6*|6
.91
1.77
1*|2
3*59
1*21
A* a 3
3*70
1*50
4-66-
1.17
1 .61
.25
• 11
.23
• Ml
1.31
1 . II
__M.M$_
2.87
t'si"
- 1*7Z
2.61
_L**J_.
1.01
             A-13  POLLUTANT-12128 Lead
                   METHOD-92 Hi-Vol Atomic Absorption
                   UNITS-01  UG/CU Meter (25C)
                   SAMPLING INTERVAL-7-24  Hour Data

-------
                                                                                            ARITHMETIC    GEOMCTRIC
                                                                                            M£JJJ	cJ.D	MEAN	.5 JO-

CALl^ORNl A -
LOS AN&EUES
OB11B0003A05 OCTH-MARS
APRS-SERB
_Q£ T ^ — H A ft A

101 ID - rlo- '10 	 ,50-1.00 	 1. 70 --2.-30 -2.8Q — 3.89 — 5«20 — *«-30 	 7-«-*0 	 »«30 	 2-«-?0 — 2»g59 (.61 2.21-
173 LO .10 «20 .20 «30 .30 .10 .50 .60 '80 1.10 3.20 5.20 "47 ,6'l8 .28 2.73
• -»'* in ^« .ijn in i.n« i_^« i_7rt 9-ln 4.0. 1.7n 14. CA R.7n J..4n I.7H laU.^B I.IH 2.06
APR6-SEP* |68 LO ,lo .20 .20 .30 .30 .10 .50 .60 «80 1-20 2.90 7.60 «H8 .687 .27 2.S8
	 	 OCT6-MAR7-- 138 	 .10 .10 —-.60- .90- |.«0 -1.90 --2. tO — ». 1 0 — 3.7(j---««90 — S.70 	 7*00 — 7*00 — — 2^-2* 	 1 . 727- —| .79- .-1 . 97_
APR7-SEP7 |09 10 .20 «20 ,20 .30 .30 .10 .10 .60 -80 1'20 2.50 7.90 «50 .808' .27 3.09
- OCT7-MAR8 66 	 .10— -.30 - .50 ,60 .80 1 .00 I « 30 ~--Z .00 3.00 - * • 20 -S.OO — »«*0— 1 0-«JO— -4-«*0 — 4- »9»S— .4-..20 — Z«-15—
NOTINRNfiE 1 .10 .10 .10 .10 .20 ,20 .20 .20 .2o l«10 1.10 I.HO |.10 »17 ,618 .29 2.7l
LOS ANGELES
OSH1B0005AOS OCTH-MAR5
APR5-SEP5
- OCT5-MAR*
APR6-SEP6
	 	 -OCT6"MAR7
APR7-SEP7
OCT7-MAR8
NOTINRNGE
^9 - LD -2.00 H. 50 6,80 6.90 7.50 8 . 30 - 8 . 70— 9 .3o - -9 • 80 -4-1 .20- tS .4-0—1 5*1-0 	 7-M}A- — 3*f29---4.MA 1.53-
173 .50 5. HO 5.80 6.20 6.6Q 7.10 7.60 8.90 lo«6Q ll«90 13.00 |5.20 16.30 7>98 2«693 7.54 1.39
120- '20 3.*o 5.20 5.9Q 6.20 6-50 • 7.10— -7.80— B.Bfl 9 . 70 -14 . 2O --J.J • 5Q--4 &. JO 	 A-«-S* — 2,^o9--4.it2 -|,13_
165 1'20 1.2Q 1.60 1.90 5.3Q 5.80 6.20 7.30 fl.Afl 9«"<0 9.9Q 10.10 12>50 6'3l 2-050 6.QO l«37
j-*7- 	 1-00 "-^g 	 '•~2Q- ^~r«G — ^-8g_ Ji-Sfl 9,10 '-"0 IQ-BO 11*30 l'-»0 ["-"O '9-ln K.JA .. j.j.19 7.71 ]«17
|08 LD 8. HO 9.50 10.30 IQ.'O 11.30 11.60 11.90 12'*0 |3«60 11.7Q 16.80 17.50 ll'O9 2.298 10«8* l»23
62 (.10 3.8o - 5.30 7. 10 8 . 30 9 , | 0 -.9-. 40 1 0 .60 -!-(-. SQ— 1 3,* 20 -i-300 — H*7-0_l-3.-90 	 8 «-S8 	 3t|8Z_-8«Ot It13_
5 9.10 9.1o 9.10 9.20 9.20 9.70 9.70 9.90 9.9Q 10*10 10.10 10»10 10«10 9«60 .H3A 9.59 1 «OS
C - fr 	 OCTH-MAR& 	 H7 	 6*8Q— lr6Q«
C
C
C
C
C
C
C
-
-'
-
-
-
• .
-
ft
A
A
A
A
A —
A
APRS-SEpS
OCTS-MAR6
APR6-SEP6
OCT6-MAR7 --
APR7-SEP7
— OCT7-MAR8 —
NOTINRNGE
165
1 19
159
137
102
-&8
H
2
--3
H
u
2
— 2
7
•20-
.90-
.90-
• 00-
.50-
.90-
.70
S
1
3
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7
- 1
7
.00
• 10
.90
.70-
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.70
                           - 1 '-10	J,*O	1.50-—5.20—6-.40	*-• 5-0	7»?
                            5.50  5.9Q  6.30   6.80  7.5Q  8,HO iQ'OO 11%80 12.50 11-30  16.20   7«56  2.8S3  7>o7
                            3.60-- H.HO - H.9Q—5.30  S»7Q—^.10—7»2o	8'70--40 ^20~l-3*-2fl-4 I-. IO	&«Ji	s.o5O--S^50
                            H.10  H.HO  1-90   5.30  5.BO  6.80  8-lp  9.00  9.50 10-00  I2«50   5'83  2«295  5.H3
                            3.HO  H.50  5.30	6.10 —-7 >^0—8.60—9-.3o~fO«10-l I-«OB—1*-«50—25« l&	6^22	3.9*6 -5.25
                            9.QO  9.80 lO'SQ  10.60  11.00 11.HO I2«2o (3.20 13.9p 15.3Q  16«8Q  lo*53  2.H82 10"21
                            J.-7-0-7—S-.-50-	4«5o	7 .40—8-.00—9.30—4-S»2g—H • SO—li»Si-9B.
                            7,70  7.70  9.10   9.10  9.10  9.50  9.So  9.70  9.7Q  9.70   9.70   9«QO   .902  B.96
• 16
.79
.26
.6?..
•It
A-14   POLLUTANT-12128 Lead
        METHOD-01 Hi-Vol Atomic Absorption
        UNITS-01  UG/CU Meter (25C)
        SAMPLING INTERVAL-3-04  Hour Data

-------
YEAR
NUM
— LOS ANSfLES — 	
051180003AQ5 APRS-SEpS 23
	 OCT5-MA«6 	 39-
APR4-SEP6 107
APR7-SEP7
NOTINRNfiE
LOS ANGELES
OCTS-M4H4
OCT4-MAB7
OCT7-MAB8
NOT 1 NRNfiC
— • C - A APRS-SEPS
Q 	 C__ t 	 -OCTS-HAR* 	
1X3 C - A APR4-SEP6
r ™ JL nj" T i u & c, 7
C •- A APR7-SEP?
C * A OCT7"MAw8
C - A NOT1NRNGE
165
—61-
2

11
T03-
103
61
'
23
-37-
lOO
|53
1
WIN 10
•00 .21
	 .00 	 .30
.00 .00
.00 .09
	 * 00 	 *-| '7—
•00 .00

— T*52 	 1.59
1.20 5.35
—S*I2 	 Bi-37"
.00 2.9l
10*13 10.1^
1.41 1.7s
	 rJB- — 3.15~-
S.52- 1.12
,,»«-* oa ••— 1- ••-*•«—-
1>83 8.23
-\ -7 » 9 7 w- — rS fi **
10*13 10.13
20 30 HO

.38 .11 .59
- — . 5-7 	 -, 4 9 	 r9-7 -
.17 ,23 .29
.15 ,21 .25
.00 .00 .00
50 60 70 8ii 90 95

.68 .81
--ti3Q— t-.IB
.33 .11
.28 .31
1.07 1*22
.00 .00
— 4-rftQ 	 7-.-40 	 T-r8 4 — *T7 3 — ^ rW
5.4' 6,17 6.81 8.07 9.22
— 5 .21-— S.74— - 4. 18-- 4,9&-— 7*66
7.93 8.97 1Q.13 11.36 12.11
T 0"*"0 5— TO . 9 1~T1 .-3-3- T T> 8 *~ T2"*"1 3
5.57 6.87 8.28 9.35 10*25
iy*l3 10*13 IIH13
6*27 6.38 6.9Q
— «|-r03 — -5'. 19 	 5-r70-
1.74 5.25 5.87
9.15 10.19 11 .03
10*13 10.13 10*13
TU*IJ 1D,IJ
7.73 8.51
— frrTT- — *.9*
6.SQ 6*97
11.16 u .99
10.13 10.13

.83 .8)3
— 2.19 	 2'*7
.51 .5«

1.31 2.33
— 5.02 — 5.3 a~
.90 1.11
.39 ,1S .41 .77
— ?»03 	 3 . 1 3—- «t-r»6 — 5-^52-
•oo *0g oo
— 13*|4 n-rt;
10*06 10*8^
12.72 13*85
- I2*75-T3v2i
I0«70 11.6J
10.13 10'13
12.39 lz*9,
	 T-j-3-9 	 8.114
7.88 9. 13
11.57 \y, 5 ,
12.13 12. 7^
- 9o« lp, 2T
10.13 10*13

|5»76 1 8«21
12*00 12.90
- I) »38- 13.01-
|1.19 16.01
Il«0* lt-f-76-
12-62 13.60
10*13 10*13
|L28 15*26
-tO-«-67 11 .07-
1 1 «18 13*01
13*78 11*10
~1 1 »-5t- 13.36
10*13 10*13
99 MAX
3.99 3.99
-5.15 5. IS- —
7.74 8.81
	 » i tO 	 fr .4-7 	
1.18 2.22
10-»13 13.33 — -
.00 ,00
T «-r2-3— 1 8 « 2 3 	
11.52 11.52
11.63 16.41 - -
17.12 17.60
15.38 18.00 —
11.66 15.22
10.13 (0*13
17.10 17.10
1ST |2- 13, 1 2 	
11.21 16. tl
15.13 I7.9Q
-13.58 H.6J -
10.13 10.13
• "iinwtTit.
MEAN STD
• 86
"1 •»»
• 61
-T-97
• 00
ro'ft
8«27
7«l8
10>66
10'l3
9*11
6«65
4«9S
11-28
10«l3
.833
	 1 l46Q
1.186
	 t-s*4^
.301
• 000

1 *075
2.973
-•-2.710-
3.828
-2-162
• oOD
3-671
-••2.79*
3-1 18
2.|88
MEAN STD
.62
— !».)•»
.28
.00

7.78
-7.02
-ti'is
8. 08
1 0 • 1 3
8.73
- 6 . 1 1
4*31
ll«07
-5.15
I0> 13
2.25
-j.|Z -
3.1»
— r.-to—
2.13
-9 JL U
1. 00 -

- .ij-
.12
••- .20 -
.19
1 • 00
1.18
— -I--.SO-
1-53
l'2|
1 <00
A-15  POLLUTANT-12128  Lead
      METHOD -98 Membrane X-Ray  Fluorescence
      UNITS-01 UG/CU Meter (25 C)
      SAMPLING  INTERVAL - 3-04 Hour Data

-------
O
OJ
                                                                           on
                                                                                         MAX
                                                                                              ARITHMETIC   GEOMETRIC
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                      METHOD-91  Hi-Vol Colorimetric
                      UNITS-01 UG/CU Meter (25 C)
                      SAMPLING INTERVAL-7-24  Hour Data

-------
                                                                                                           A*ITHMET|C
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            A-17   POLLUTANT-12403 Sulfate
                    METHOD-91 Hi-Vol Colorimetric
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                    SAMPLING  INTERVAL-3-04  Hour Data

-------
                                        20
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              UNITS-01  UG/CU Meter (25 C)
              SAMPLING INTERVAL-3-04  Hour Data

-------
o
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YEAR
CAL IFORNl A
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                   METHOD-92 Hi-Vol Sodium Phenolate
                   UWTS-01 UG/CU Meter (25 C)
                   SAMPLING INTERVAL - 7-24 Hour Data

-------
YEAR
CALIFORNIA
-LOS AN6EL€5 •— 	
051180003A05 APR1-SEP1
APR5-SEP5
APR6-SEp6
APR7-SEp7

051180005AQ5 APR1-SEP1
APR5-SEPS
APR6-5EP4
APR7-SEP7
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C - A APR1-SEP1
C.- ApRg-sEpS
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-------
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-------

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-------
                                    TECHNICAL REPORT DATA
                             (Please read Instructions on the reverse before completing)
  REPORT NO.
  EPA  600/4-79-033
                                                            3. RECIPIENT'S ACCESSION-NO.
 4. TITLE AND SUBTITLE
  Los Angeles  Catalyst Study
    Annual  Report
                            5. REPORT DATE
                            __May 1979^	
                            6. PERFORMING ORGANIZATION CODE
  . AUTHOR(S)

  Gary  F.  Evans and Charles  E.  Rodes
                                                            8. PERFORMING ORGANIZATION REPORT NO,
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Environmental Monitoring  and  Support Laboratory
  Environmental Protection  Agency
  Research Triangle Park, N.C.  27711
                            10. PROGRAM ELEMENT NO.
                               1AA601
                            11. CONTRACT/GRANT NO.
 12. SPONSORING AGENCY NAME AND ADDRESS
                                                             13. TYPE OF REPORT AND PERIOD COVERED
                                                             14. SPONSORING AGENCY CODE
                                                               EPA 600/08
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT

  This  report is a summary  of  the data collected  at  the Los Angeles  Catalyst Study
   (LACS)  from June 197*t  through December 1977-  Previous reports of  the LACS data
  were  presented at the  symposium held in April 1977,  covering the data through
   1976.   The current report follows the same data presentation format,  showing
  6-month average trends of the summer seasons  (April  through September)  beginning
   in  197^-   Additional graphs  are included in this report giving more  detailed
  comparisons of freeway pollutant contributions  with  traffic parameters.   Also
   included are method comparisons of high volume  and membrane samplers  for total
  mass,  SO,,  Pb, and ratios  of
S/SO^ and Pb/Br.
 17.
                                 KEY WORDS AND DOCUMENT ANALYSIS
                   DESCRIPTORS
              b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
  Ambient Air  Monitoring
  Air Pollution
  Aerosols
  Traffic
  Meteorology
  Sulfates,  Lead,  Carbon Monoxide
                 Los  Angeles
                 San  Diego Freeway
                 Catalytic Converter
   68 A
   43 F
 8. DISTRIBUTION STATEMENT

 Release to  Public
               19. SECURITY CLASS (ThisReport)
                 Unclass ified
21. NO. OF PAGES
   119
               20. SECURITY CLASS (Thispage)
                 Unclass if ied
                                                                           22. PRICE
EPA Form 2220-1 (9-73)
             110

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