receiver coated with Parsons optical black lacquer. The instrument was attached to an electrically driven equatorial mount for solar tracking. TEMPERATURE.
EPA-600/7-78-053
March 1978
NITROGEN DIOXIDE PHOI'OLYTIC, RADIOMETRIC and METEOROLOGICAL FIELD DATA
by
J.E. Sickles II, L.A. Ripperton, W,C. Eaton, R.S. Wright Research Triangle Institute Research Triangle Park, North Carolina
27709
Contract No. 68-02-2258
Project Officers Joseph J. Bufalini Bruce W, Gay, Jr. Atmospheric Chemistry and Physics Division Environmental Sciences Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
DISCLAIMER
This report has been reviewed by the Environmental Sciences Research Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use.
ii
ABSTRACT
Photolysis of nitrogen dioxide is the major reaction resulting in the formation of ozone in the troposphere.
Under ambient conditions, k , the 1 rate constant for the photodissociation of N0 , is a function of solar 2 altitude and cloud cover and, therefore, is highly variable. The objective of this study was to collect k , radiometric, and se1 lected meteorological data over periods of several days under a variety of meteorological conditions. of 1975.
Data were collected during the spring and fall
Eight days of data were collected between 21 April and 30 April.
The time resolution of these data was 10 minutes for 6 days and 5 minutes for the remaining 2 days.
Between 3 October and 31 October, 13 days of data
were collected with 1-minute time resolution.
Data from this study are
needed to aid the modeling of tropospheric photochemical air quality and smog chamber results. This report was submitted in fulfillment of Task C of Contract No. 68-02-2258 by the Research Triangle Institute under the sponsorship of the U.S. Environmental Protection Agency.
This report covers a period from
June 30, 1975, to June 30, 1977, and work was completed as of July 31, 1977.
iii
iv
CONTENTS iii vi vi
Abstract Figures Tables . Acknowledgments
vii
1.
Introduction Background Objectives
1 1 1
2.
Summary and Recommendations
2
3.
Experimental . . . . . . . Description of the k Device 1 Radiometric Instruments . . Temperature . . . . . . . . Meteorological Observations Measurement Program Site Description Data Acquisition Procedure
5 5 10 12 12 13 13 15 15
4.
Results . Data Error Analysis
17 17 19
References
21
Appendixes
22
A. B.
c.
D.
April 1975 k and Radiometric Data 1 April 1975 Local Climatological Data October 1975 k and Radiometric Data 1 October 1975 Local Climatological Data
v
23 41 45 181
FIGURES Number 1
2
Flow diagram of 1-liter quartz globe CSTR for nitrogen dioxide photolysis rate measurements . . . . . .
6
General layout of the data collection site in Research Triangle Park, North Carolina . . . . . . . . . . . .
14
TABLES 1
Swnmary of Input Data
11
2
Characteristics of Radiometric Instruments
12
3
Summary of Measurement Program
13
4
Summary of Environmental Data
18
vi
ACKNOWLEDGMENTS This project was conducted by the Research Triangle Institute under Task C of Contract Number 68-02-2258 for the U.S. Environmental Protection Agency.
The support of this agency is gratefully acknowledged as is the
advice and guidance of the EPA personnel who contributed to the project: Dr. J. J. Bufalini who served as Project Officer, and Drs. Basil Dimitriades and Ken Demerjian who initiated the project.
The helpful and cooperative
discussions with Dr. Ken Demerjian, Dr. Jim Peterson, Mr. John Rudisill, and Mr. Ken Schere are also appreciated. Many people at the Research Triangle Institute contributed substantially to this project. project.
Mr. Cliff Decker was Laboratory Supervisor for the
Mr. Dennis Ewald, Mr. Dave Dayton, and Mr. Bob Murdoch conducted
the day-to-day measurements in the mobile laboratories.
Mrs. Sandra Burt,
Mrs. Debbie Miles, and Mr. Jerry Smith were instrumental in transferring the collected data into computer-compatible format. We gratefully acknowledge these individuals for their efforts in bringing this project to a successful conclusion.
vii
SECTION 1 INTRODUCTION BACKGROUND The photolysis of nitrogen dioxide (N0 ) is considered to be the pri2 mary stimulus to chemical change for photochemical air pollution systems. It is the major, if not the only, reaction resulting in the tropospheric formation of ozone.
The rate constant for the photodissociation of N0
2
is
usually represented as "cl>ka for N0
11 or simply as "k 11 • Continuous k data 1 2 1 are needed to aid the interpretation of photochemical air quality data and
as input for computer models of smog chamber results. Under ambient conditions, k
is not constant. It is a function of the 1 sun's position in the sky and thus is dependent on time of day, season of year, and geographical location.
Variable atmospheric conditions, such as
cloud cover and aerosol loading, influence ambient sunlight intenoity and thereby preclude the accurate prediction of k the day.
over the sunlit portion of 1 Although continuous radiometric instrumentation is available for
determining both ultraviolet (UV) and total solar radiation (TSR), relationships between measurements with these instruments and chemically meaningful light intensity are not well established.
OBJECTIVES A device has been developed by Sickles and Jeffries 1 to monitor k , the 1 rate constant for the photodissociation of N0 . The purpose of the task 2 described in the present document was to collect 21 days of ambient k data 1 using the technique of Sickles and Jeffries. 1 Each day's measurements were to be collected from sunup until sundown.
In addition to the k
data, 1 radiometric data and meteorological conditions were also to be recorded.
The scope of this task was limited to data collection; the analysis and interpretation of the results are, therefore, deferred to future studies. 1
SECTION 2 SUMMARY AND RECOMMENDATIONS The objective of this study was to collect several days of ambient k , 1 radiometric, and selected meteorological data under a variety of meteorological conditions. A total of 21 days of data was collected during spring and fall measurement periods in 1975. April and 30 April.
Eight days of data were collected between 21
The time resolution of this data was 10 min for 6 days
and 5 min for the remaining 2 days.
Between 3 October and 31 October, 13
days of data were collected with 1-min time resolution. The estimated precision of the k is
~8
percent.
determinations in the present study 1 This can be improved substantially by improving the preci-
sion of gas flow rate control. could satisfy this requirement. future k
1
It is suggested that mass flow controllers This approach should be considered in
measurement programs that employ the technique used in the present
study. The data from this study are needed for two reasons: 1.
To provide much-needed kinetic information to modelers of polluted atmospheres and smog chambers.
2.
To provide a data base for correlating ambient k
1
measure-
ments with solar radiation data as determined by conventional radiometric instrumentation. It is recommended that the data compiled in this study be analyzed in detail.
Correlations of k
and radiometer data should be made. Such analyses 1 would allow future and historical radiometric data to be applied directly in airshed modeling. The following recommended approach would involve statistical analyses of data collected over different time scales.
2
1.
The data should be stratified into hourly and daily data sets. Regressions should be compared for each hour of every measurement day.
These should also be compared with overall regressions for
each corresponding measurement day. 2.
Day-to-day comparisons of k
data should be made to examine the 1 effects of local weather conditions such as clear versus overcast sky conditions.
Other atmospheric factors that may change con-
siderably from day to day include ozone column, water vapor concentration, and haze or particulate loading.
The influence of
these factors on ambient k
3.
data should be explored. 1 The data from the spring and fall measurement periods should be compared.
From this analysis, trends indicative of seasonal
behavior may become apparent.
In addition, overall regressions
for the measurement period should be compiled. In addition to analyzing and interpreting the data collected in the present study, it is recommended that a more extensive measurement program be undertaken.
Such an effort would have two major goals:
to develop an
extensive data base at a single ground station and to measure the dependence of k
on vertical altitude. The first phase of the program would require 1 collecting and archiving k , radiometer, and meteorological data at a single 1 ground station over at least a 1-yr period. This effort would establish a
sufficient data base for statistical analyses.
Not only could the types of
statistical data analyses suggested previously be conducted, but additional tests to isolate seasonal effects could be performed as well. The second phase of the program would require mounting the k
device on 1 an aircraft and collecting actinic flux data as determined by this chemical actinometer at altitudes up to 10 km.
Atmospheric aerosols contribute sig-
nificantly to the optical thickness of the atmosphere.
This is particularly
evident near the earth's surface where these aerosols are highly concentrated.
It has been suggested recently from model predictions that this
phenomena may be responsible for a marked increase in actinic flux with altitude through the lowest few kilometers of the atmosphere. 2
These pre-
dictions suggest that the actinic flux at 1 km may be 20 to 60 percent larger than that at the surface of the earth.
This should be verified by a
field program employing an airborne measurement platform.
3
An alternate approach might employ ground stations located on a mountain top and in a nearby valley.
Although this approach may not address the
question at hand as specifically as the airborne program, it would be simpler to implement.
4
SECTION 3 EXPERIMENTAL DESCRIPTION OF THE k
1
DEVICE
This subsection describes the operation of each of the two k employed in this study.
devices 1 For more details concerning the theoretical devel-
opment of the technique, the original paper 1 should be consulted. Apparatus A schematic of the k
device and gas delivery system is presented in 1 Figure 1. A stream of approximately 37 ppm N0 in nitrogen was blended with 2 a nitrogen stream to yield a nominal concentration of 1.5 ppm. Commercially prepared cylinders of N0
in nitrogen (Scott) and oxygen-free nitrogen 2 (Matheson) were used. The N0 -N delivery system consisted of the following 2 2 hardware: gas cylinders, dual-stage stainless steel diaphragm pressure regulators, stainless steel precision needle valves, Teflon mixing tees, and 3.2-mm ID Teflon tubing.
Forty-five-meter lengths of 2.5-cm ID black PVC
tubing were employed as light-shielded umbilical cords. the 3.2-mm Teflon feed and effluent lines.
Each cord contained
The umbilical cord served to
connect its flask with the remainder of the gas delivery system and the NO analyzer that were housed in a mobile laboratory. 1 liter/min was maintained.
x
A nominal flow rate of
This corresponds to a 20-s residence time from
the flask to the NO
analyzer. Flow rate from the effluent line was measx ured periodically with a wet test meter.
Nitrogen Oxides Analyzer Two Bendix Model 8101-B Oxides of Nitrogen Analyzers were employed in the study.
A separate instrument was used to monitor the NO and N0
trations from the effluent lines of each of the two k
concen2 The prin-
devices. 1 ciple of operation employs the chemiluminescent gas-phase reaction between
5
hv
I Quartz Globe Volume -1 Liter
••------::i•-"
To Second Device
Needle
Teflon Mixing Tee
\
Light
Shield•e~~~.....,•-
-1. 5 ppm N02
-1000 cc/min
To Second Device
3.2 mm ID Teflon Tubing
)lt=-1 -1000
cc/min
Needle
~Valves
-150 cc/min -37 ppm
N0
2
in
N2
NO
x
Analyzer
Waste
Figure 1.
Flow diagram of 1-liter quartz globe CSTR for nitrogen dioxide photolysis rate measurement. 6
NO and [N0 ]. 2
o3 .
Two modes of operation are required to determine both [NO] and
Nitric oxide concentration is determined first using the reaction
o3 .
between NO and reduction of N0 duction of N0 be the NO
2
The determination of [N0 ], however, requires catalytic 2
to NO prior to the reaction of NO with ozone.
to NO, the signal from the total NO in the sample is taken to
2
concentration.
x
After re-
Electronic subtraction of the original NO signal
from the NOx signal gives the N0
2
In the normal "NO-NOx -NO 2 ' N0 and NOx concentrations
concentration.
mode, the instrument operates on a 1-min cycle:
2
are updated at the end of the first 30-s interval and the NO concentration is updated at the end of the second 30-s interval. high concentrations of N0
2
such as that from the k
formance of the reducing catalyst to deteriorate.
Continued exposure to device causes the per-
1
The instrument was,
therefore, operated primarily in the "NO only" mode. "NO-N0x-N0
11
2
Brief operation in the
mode once every 3 to 6 h verified the constancy of the NOx
concentration from the k
device and thus allowed determination of the N0 1 2 concentration at any time by a mass balance calculation. The analyzer was operated on a range of 0 to 2 ppm with a minimum detectable concentration of 0.005 ppm. Theory A mixture of N0
2
in nitrogen was fed to a spherical quartz continuous
stirred tank reactor (CSTR) of volume, V, where light of the appropriate wavelengths caused the N0 and NO and N0
2
to photodissociate.
The measured flow rate (Q)
concentration levels in both the CSTR feed and effluent
2
streams may then be transformed by Equation 1 to a k
1
value.
Equation 1
applies for constant temperature conditions only. ll[N0 ] 2
kl
. 2T [N0 ] 2
[N0] [1 + R 1 + R 2
0
+ ti[N0 2 ]
[N0 ] 2
J
(1)
where t.[N0 J 2
[N02]o [N0 ] 2
=
decrease in [N0 J due to reaction
=
concentration of N0
=
concentration of N0
2
2 2
= [N02 ] 0
in the feed stream in the effluent stream
7
-
[N0 ] 2
[NO]
0
[NO] t
=
concentration of NO in the feed stream
= =
concentration of NO in the effluent stream residence time in the reactor
= V/Q
(Note that if flow rate is measured at laboratory temperature (298°K) and the reactor is at a different temperature (T°K), then the temperature correction factor (298/T) must be applied to correct the residence time)
V
Q R 1
= =
flask volume
=
ratio k 1 [M] /k" for the following two reactions:
flow rate
0
k'
+
N0
=
2
+
M
~ N0 3 +
M
1.0 x l0- 31 cm 6 molec- 2 sec
-1
k"
k"
=
• NO + o 2 9.1 x 10- 12 cm3 molec-l sec-I
Both k 1 and k" are reported to be independent of temperature. 3
The temperature dependency of the
third body concentration ([M] = [N ] = 2.463 x 10 2 molec cm- 3 at 298°K) may be incorporated into the
19
following expression for the dimensionless ratio, R :
1
R 1
R 2
=
= 80.664/T
Note that at 298°K, R 1 ratio k'"[M]/k" 0 + NO + M
k
I II
• N0
2
+
= 0.27. M
k I l l = 4. 2 x 10-33 e940/T cm6 molec -2 sec -1
8
The temperature dependency of both the third body concentration and k'" may be incorporated into the following expression for the dimensionless ratio,
R2:
3.3879 940/T T e
R2
=
Note that at 298°K, R 0.27. 2 A mass balance on nitrogen oxides (NO ) for the CSTR may be written. x
[NO]
0
+ [N0 2 ] 0 = [NO] + [N0 2 ] = [NO x ] = constant
This expLession may be combined with Equation 1 to arrive at Equation 2. Equations 1 and 2 apply only for constant temperature conditions. ([NO] - [NO] ) 0
2T ([NO ] - [NO]) x
[NO] ] [ l + Rl + R2 [NOx] - [NO]
(2)
Equation 3 may be derived for variable temperature conditions by substituting the temperature-dependent expressions for R and R and the temperature1 2 corrected expression for t into Equation 2. Equation 3 is the formula used in this study to calculate k . 1
( [NO] - [NO] )
80.664 + 3.3879 e 940/T T T
0
2 T ( [NO ] -
x
[NO])
[NO] ] [NOx] - [NO]
(3)
Calculations Raw nitrogen oxides concentration data for both the spring and the fall measurement periods were corrected by applying the appropriate span and zero correction factors.
The other input data that are required for the calcu-
lation of k
were assumed to be constant for each measurement day: flask 1 volume, initial NO concentration, volumetric flow rate, and total NO conx
centration.
The flask volume is constant.
The [NO]
0
was generally small:
Mean values of Q and [NO ] were determined for x Relative percent variations (%RV), i.e., percentage
between 0.00 and 0.02 ppm. each measurement day.
of the average constituting the range, were also calculated for Q and [NO]. x The required input data (V, [NO] , Q, and [NO ]) for each measurement day 0 x 9
are presented in Table 1 along with %RV for Q and (NO]. x ations were generally less than 7 percent.
Relative vari-
For both measurement periods, ambient air temperature data were asswned to be representative of flask effluent conditions and were employed in the k
computing formula, Equation 3. In the event of missing temperature data, 1 default temperatures interpolated from the 3-h data collected at the Raleigh Durham Airport (RDU) 4 were employed. RADIOMETRIC INSTRUMENTS Radiometric instruments were provided by the EPA Division of Meteorology.
These instruments were positioned on an 8-m-tall wooden platform.
Data from four radiometers were collected during both the spring and fall measurement periods.
The operating characteristics of these four instru-
ments are summarized in Table 2.
The following paragraphs provide a brief
description of each instrument.
A more complete description of each instru-
ment is presented by Coulson.
5
The Eppley Precision Spectral Pyranometer is used to measure total solar radiation and can also be used with various Schott optical filters to measure ultraviolet radiation and solar radiation in selected spectral bands.
The sensing element is a thermopile of copper electroplated on
constantan wire over one-half of each turn of a wire-wound thermopile. In this study two such devices were employed: (TSR) and one with a 395-nm filter (395).
one with a 295-nm filter
Total solar radiation was deter-
mined by the first device using a clear WG7 Schott filter.
The second
device employed a Schott GG 395 filter for the determination of light intensity at wavelengths longer than 395 nm.
Although the difference between the
TSR and 395 outputs was not calculated in the present study, this value should correspond closely to that of the ultraviolet sensor. The Eppley Ultraviolet Radiometer (UV) is designed to measure global flux in the near ultraviolet region (295-385 run).
The sensing element for
this device is a Weston selenium barrier-layer photoelectric cell. The Eppley Normal Incidence Pyrheliometer (NIP) is used to measure direct solar radiation.
The sensing element is a fast response wire-wound
plated (copper-constantan) multijunction thermopile with a 9-mm-diameter
10
TABLE 1. Lunar date
Julian date
SUMMARY OF INPUT DATA
Va (cm 3 )
[NO] 0 ppm
Qb (cm 3
min
-1
)
%RVc
[NO ]d x
%RVe
4-21-75
111
1174
0.012
886
2.9
1.707
1.3
4-22-75
112
1174
0.014
887
2.3
1.646
2.6
4-23-75
113
1174
0.010
902
0.6
1.490
1. 1
4-25-75
115
1174
0.011
897
1.2
1.586
1.2
4-27-75
117
1174
0.005
900
0.3
1.520
3.0
4-28-75
118
1174
0.011
915
0.7
1.474
2.0
4-29-75
119
1174
0.011
898
1.3
1.233
0.3
4-30-75
120
1174
0.015
922
3.2
1.228
7.2
10-10-75
283
1185
0.004
1005
1.6
1.064
ND
10-12-75
285
1185
0.000
1026
5.7
1.032
ND
10-14-75
287
1185
0.000
1027
2.7
1.033
ND
10-16-75
289
1185
0.002
1053
3.1
1.024
ND
10-20-75
293
1185
0.000
1094
6.3
0.969
ND
10-22-75
295
1185
0.002
1117
3.3
0.898
ND
10-23-75
296
1185
0.000
1131
7.1
0.914
ND
10-24-75
297
1185
0.002
1129
3.6
0.969
ND
10-27-75
300
1185
0.006
1126
3.2
0.885
ND
10-28-75
301
1185
0.020
1122
3.0
0.874
ND
10-29-75
302
1185
0.004
1104
5.5
0.887
ND
10-30-75
303
1185
0.012
1116
3.0
0.952
ND
10-31-75
304
1185
0.015
1105
3.9
0.869
ND
aVolume of flask. b
Mean value of flow rate over measurement day.
cRelative percent variation for Q, i.e., [(range x 100) ~ mean]. d Mean value of [NO ] over measurement day. x eRelative percent variation for [NO]; ND= not determined. x
11
TABLE 2.
CHARACTERISTICS OF RADIOMETRIC INSTRUMENTS
Designation
TSR
UV
NIP
Manufacturer
Eppley
Eppley
Eppley
Eppley
Model
Precision Spectral Pyranometer
Precision Spectral Pyranometer
Ultraviolet Radiometer
Normal Incidence Pyrheliometer
Operating principle
Thermopile
Thermopile
Photoelectric cell
Thermopile
0-2800
0-2800
0-70
0-2800
Sensitivity, -2 mV/(W m )
9
9
150
8
Response time, s
1
1
10- 3
1
Range,
a
-2 Wm
395
al Langley= 1 cal cm- 2 ~ 700 W m- 2 receiver coated with Parsons optical black lacquer.
The instrument was
attached to an electrically driven equatorial mount for solar tracking. TEMPERATURE An ambient air temperature monitoring instrument was provided by EPA. Air temperature was determined by a thermistor located in a Gill Aspirated Temperature-Radiation Shield.
Measurement errors are within +0.05° C.
Ambient air temperature data are reported for both the spring and the fall measurement periods. METEOROLOGICAL OBSERVATIONS The meteorological conditions for the measurement days are characterized by such data as cloud cover, visibility, temperature, and relative humidity.
These and additional environmental data are collected by the
National Weather Service at RDU. 4
The measurement site for the present
study is located within 8 km of RDU.
Meteorological conditions at RDU are
considered to be generally representative of those existing at the measurement site and therefore are reported in this study.
12
MEASUREMENT PROGRAM Data were collected during the spring (April) and again during the fall (October) of 1975.
The types of measurements that were conducted during each
period are swnmarized in Table 3. SITE DESCRIPTION Data were collected near a building on Davis Drive in Research Triangle Park, North Carolina, which houses part of the EPA Division of Meteorology. The general layout of the site is illustrated in Figure 2. Two instruments were employed in this study to measure k . One of these 1 devices designated as "Flask A" or the "Platform Flask" was normally located on an 8-m-tall wooden platform that also supported a battery of radiometric TABLE 3.
SUMMARY OF MEASUREMENT PROGRAM Spring 1975a
Fall 1975b
.j
d
d
.j
TSR
.J
~!
395
.J
.j
UV
.J
.j
NIP
.j
.j
Ambient temperature
.J
.J
.j
.j
NO, N0 , NO (Flask A) x 2
c
NO, N0 , NO (Flask B) 2 x
Meteorological conditions a
b
c d
e
e
Measurement period April 21-30, 1975; note that time resolution was usually once per 10 minutes. Measurement period October 3-31, 1975; note that time resolution was once per minute. For k
determinations. 1 Data from this instrument were invalidated due to NO instrument drift x and anomalous behavior. Meteorological conditions were reported for each measurement period by the U.S. Weather Service at the Raleigh-Durham Airport. 4 13
DAVIS DRIVE
N
60 m
Flask
40 m
(5 m Tall)
Umbilical
\~Cord __ ....... •Flask B \
EPA Building
8 m Tall /Platform
y
(L] 8 m
\
...... , ...
_._.-._,re.------
...
Trees
(12 m Tall)
2om--..
\ Mobile Laboratory
55 m
Parking Lot
Figure 2.
General layout of the data collection site in Research Triangle Park, North Carolina.
14
-
sensors.
This flask was positioned at the center of a flat, 1.5 m x 1.5 m
syuare surface that had been painted with optical black paint.
This config-
uration was chosen to limit the view angle of the k
sensor to the skyward 1 hemisphere by blocking reflected light from the earth's surface. The second of these devices, designated as "Flask B" or the "Tower Flask" was suspended by a 2.5-cm-diameter pipe over a grassy area. angle of this flask was essentially 360°.
The view
The nearest obstruction was
approximately 20 m from the device. DATA ACQUISITION During the spring measurement period, the nitrogen oxides concentrations determined by instruments housed in a mobile laboratory were recorded on strip charts (see Figure 2).
Subsequently, these records were
manually reduced into the form of 1-min average values at 10-min intervals for each measurement day.
This 10-min NO
data set was then computerized. x Instantaneous radiometric and ambient air temperature data were ac-
quired at 1-min intervals by a Digitem automatic data acquisition system. This data system was maintained by the EPA Division of Meteorology for the purpose of archiving local environmental data.
The 1-min radiometric and
temperature data were computerized and then machine-sorted. at the same time as the NO
The NO
data and the corx responding radiometric and temperature data were then merged into a single
x
data were retained.
Data collected
computerized raw data set for the spring period. During the fall measurement period, all the raw data (nitrogen oxides concentration, radiometric, and temperature data) were acquired by the EPA data system at 1-min intervals over each measurement day.
Backup strip
chart records were also maintained for nitrogen oxides concentrations and radiometric data.
The I-min data were subsequently computerized into a raw
data set for the fall period. PROCEDURE Zero and span settings of the NO
analyzers were adjusted prior to dawn x or on the evening before a measurement day. Calibrations for NO and NO x were established by dilution of a certified cylinder of NO in nitrogen. Calibration for N0
2
was performed by using the N0
15
2
produced from the gas-
phase titration of known NO concentrations with
o3
from a calibrated ozone
generator. Nitrogen and N0
flow rates to each flask were adjusted to the nominal 2 target values prior to dawn. Initial concentrations of NO, N0 , and NOx
2 were recorded, and the effluent flow rates were determined with a wet test meter.
To prevent deterioration of the N0 -reducing catalyst, the NOx 2 analyzers were operated primarily in the "NO only" mode. Both radiometric and NO concentration data were acquired either on strip charts or by an automatic data acquisition system.
The instruments then remained essen-
tially unattended for 3- to 6-h intervals.
Between these intervals, flow
rates were measured and the NOx analyzers were operated in the "NO-NOx-N0 " 2 mode. These periodic determinations were performed to assess the variability of the flow rates and the NO
x
concentrations from each flask.
During the early morning hours, dew appeared on the surface of the flasks.
The flask surfaces were manually wiped during this period.
Time
records of the flow checks and condensate removal activities were maintained, and data for these periods were invalidated and removed from the final data set. During the spring measurement period, the position of Flask A was not fixed from day to day; whereas Flask B remained in a fixed location during both measurement periods (see Figure 2).
On 21 April and throughout the
morning of 22 April, both flasks were suspended at a height of approximately 3 m above a grassy area.
At 1310 EST on 22 April, Flask A was repositioned
at approximately 2 cm above the grassy area.
Flask A remained at this
location until it was moved to the 8-m wooden platform at 1450 EST on 24 April.
Flask A remained on the platform for the remainder of the spring
measurement period and throughout the fall measurement period. Flask B remained in a more or less fixed location during both measurement periods (see Figure 2).
From 21 April through 28 April, it was sus-
pended at a height of approximately 3 m above a grassy area.
The height was
increased to approximately 8 m at 1645 EST on the afternoon of 28 April. Data were collected on 29 April, 30 April, and throughout the fall measurement period with Flask B at 8 m above a grassy field.
16
SECTION 4 RESULTS DATA Eight days of k
data were collected using Flask A during the spring 1 measurement period, and 13 days of data were collected using Flask B during the fall period.
The environmental conditions that existed on each day of
the measurement program are summarized in Table 4. identified in the first column.
The measurement day is
The percent of possible minutes of direct
sunshine (%SS) and the percent of sky cover (%SC) are listed in the next two columns. 4
Total atmospheric ozone concentration determined at Wallops
Island, Virginia, and at Nashville, Tennessee, 6 are listed in the next two columns.
Selected meteorological observations at RDU 4 such as daily maximum
temperature, daily minimum temperature, daily mean dew point temperatures, and comments on the prevailing meteorological conditions complete the table. The [NO] and k
data for Flask A and temperature and solar radiation 1 data are compiled in Appendix A for each day of the spring measurement period.
Note that these data are tabulated at 10-min intervals for each
measurement day except 4-23-75 and 4-27-75, and 5-min data are provided for these days.
Local climatological data for April 1975 are presented in
Appendix B. Data for the fall measurement period are tabulated at 1-min intervals in Appendix C.
The values presented in this appendix are [NO] and k
for Flask B and temperature and solar radiation data.
data 1 Local climatological
data for October 1975 are presented in Appendix D. The tabulated [NO] and temperature data may be used with the input data listed in Table 1 to verify the k
1
values in Appendixes A and C.
As noted
in a previous section, Equation 3 is the formula used to calculate the k data that are tabulated in Appendixes A and C.
17
1
TABLE 4.
SUMMARY OF ENVIRONMENTAL DATA e
f
g
0 c 3
0 d 3
T max
0
382
364
19
3
-1
Clear
98
10
380
349
23
2
3
Clear
113
78
80
355
341
26
11
11
Partly cloudy
4-25-75
115
63
100
337
28
16
17
Partly cloudy
4-27-75
117
94
50
392
23
9
5
Partly cloudy
4-28-75
118
3
100
341
18
12
13
Rain, fog
4-29-75
119
30
100
342
22
12
14
Fog, haze
4-30-75
120
0
100
363
15
12
12
Fog, drizzle, haze
10-10-75
283
46
80
293
295
24
14
14
Fog, haze
10-12-75
285
100
0
306
291
23
10
11
Clear
10-14-75
287
93
10
292
285
30
12
14
Ground fog, clear
10-16-75
289
75
70
282
28
17
17
Ground fog, haze
10-20-75
293
96
20
291
293
19
4
4
Ground fog, clear
10-22-75
295
99
0
295
294
27
8
8
Ground fog, clear
10-23-75
296
100
0
296
292
27
7
8
Ground fog, clear
10-24-75
297
42
70
287
282
23
9
13
Ground fog, haze
10-27-75
300
51
70
272
266
23
12
9
10-28-75
301
46
80
254
260
23
13
13
Fog, haze
10-29-75
302
4
100
269
309
23
11
12
Ground fog, haze
10-30-75
303
85
20
306
298
16
4
3
Partly cloudy
10-31-75
304
97
40
291
290
13
0
-3
Partly cloudy
Julian Date
1,SSa
4-21-75
111
100
4-22-75
112
4-23-75
Lunar Date
iscb
= percent
T . min
TDP
Comments
Partly cloudy
of possible minutes of direct sunshine. 4 bisc = percent of sky cover. 4 cOzone column in 10 -3 STP cm measured at Wallops Island, Virginia. 6 d Ozone column measured at Nashville, Tennessee. 6 eT = maximum daily temperature, oc.4 f max T . =minimum daily temperature, 0 c. 4 min 8T p daily mean dew point temperature, oc.4 0 aiss
=
18
Two points should be considered prior to extensive data analysis and interpretation. 1.
The spring [NO ] data were reduced manually from strip chart x records. The subjective nature of this procedure may introduce some inconsistencies on comparison of the spring data with the more objective, machine-acquired fall data.
2.
The nominal response time of the k
device was over a minute. 1 Radiometric instruments have response times of approximately 1 s. This oifference in response times should be considered if precise comparisons are to be made between k
and radiometric data.
1
ERROR ANALYSIS Several factors can introduce errors into the determination of k the technique employed in this study.
by 1 These factors include errors in rate
constant ratios, nonideal mixing, temperature variation, rapidly changing light intensity, reaction in the effluent line, and measurement error.
A
complete discussion of sources of error including an error propagation analysis for Equation 1 has been presented by Sickles and Jeffries. 1
With
the exception of measurement error, the previously listed factors are thought to be of minor importance in determining the precision of the k
1
measurement. Under the assumption of constant temperature and fixed values of R and 1 R , errors enter into Equation 2 in the measurement of residence time and 2 nitrogen oxides concentrations. The residence time is subject to variations in flow rate.
Nitrogen oxides concentrations themselves may vary with
variations in flow rate from the gas delivery system.
The concentratons
indicated by the NO
instrument are subject to instrumental span and zero x drift and to deterioration of the N0 converter. The relative percent 2 variations presented in Table I suggest that ~2 percent is a reasonable estimate of 95 percent error limits for t, [NO] , [NO], and [NO]. 0
x
An error propagation analysis similar to that presented by Sickles and Jeffries 1 was performed using the ~2 percent estimates noted above.
Based
on this analysis, estimated 95 percent confidence limits on the precision of k
determinations in this study are 1 -1 +5.7 percent for a k of 0.10 min 1
19
percent for a k
-1
of 0.50 min and 1 It is suggested that these limits can
~8.8
be improved by at least a factor of two by modifying the technique to insure more nearly constant flow rates from the N and N0 cylinders. Mass flow 2 2 controllers could satisfy this requirement while simultaneously providing continuous records of flow rates for mass balance verification purposes.
20
REFERENCES 1.
Sickles, J.E., II, and H. E. Jeffries. 1975. Development and Operation of a Device for the Continuous Measurement of $k for Nitrogen Dioxide. Publication No. 396. Department of Environmentaf Sciences and Engineering, University of North Carolina, Chapel Hill, North Carolina.
2.
Peterson, J. T. 1976. Calculated Actinic Fluxes (290-700 run) for Air Pollution Photochemistry Applications. EPA 600/4-76-025, Environmental Protection Agency.
3.
Hampson, R. F., Jr., and D. Garvin, eds. 1975. Chemical Kinetics and Photochemical Data for Modeling Atmospheric Chemistry. NBS Technical Note 866.
4.
Local Climatological Data: National Weather Service Forecast Office, Raleigh-Durham Airport. U.S. Department of Conunerce, National Climatic Center, Asheville, North Carolina.
5.
Coulson, K. L. 1975. Solar and Terrestrial Radiation Methods and Measurements. Academic Press, New York.
6.
Ozone Data for the World. 1975. Atmospheric Environment Service Publication, 16. Downsview, Ontario, Canada.
21
APPENDIX A APRIL 1975 kl AND RADIOMETRIC DATA
23
kl I SlHLIGHT 11'4ff"4SllY STUDY: JUL l A•I
uATE
N ,i:..
111 11 J 111 111 11 I 11 I 111 l 11 111 111 JJ I 1 ti ll\ 111 111 llI ll 1 1l I 111 IIl lll 111 111 111 111
11 I 111 llI 111 111 1I I 111 111
111 111 11 I 111 1 tt 11 I 111 1 11 l 11 It1 111 l 11 111 111 111 11 I I 11 1 11 111
T Jl 1\45 ASS CIOS Ql5 9i?5 9JS ClllS 95"> 1005
101 S 1025 lOJS
10115 1055 1105 l llS 1125 I 135 I 1115 115':> 1205 121 r, 1225
NOA
c "c>
(l'PM}
11.89 J2.3Q l2.5b 12. 72 12.83 13.28 lJ.17 111.00 111.28 l ll .11 Ju. 55 111.01 15.oo lS.oO lS.17 is.so 15 • .59 JS.72 JS.83 1s.1111 1s. n lb.&1
o.558 u.570 o.t.os 0 0 b211 0 0 bo o.7oll o.1e.2 0 0 7S'> 0.111 0.100 o. 7711 0.111> 0.111 u. 773 o.179 0.11l
lb.ol lb.II
11.00 lo.72 1o. i.19
1235
lb.bl
12115 1255 nos 131':> 1325
11.22 17.39 1 7 .1111
1315
n11s 1355 t 110'> 11115 1az5 J II JC, 11111s 111'>5 , .. 05 1'>I'!> 15?5 IS 55
15£15 1555 l!-11'5 lb IS lt>?5
ll&t PA COloll FIACT hO.
fPIP
17. 7e
17.Qll I 7. 7t! 111.22 lA. H
o. 71Z
o.774 o. 772 o. 7711
o. 71b 0 .111 o.7bfl o.1b& 11.110
0 .1b41 0.151.1
I 7 0 941
tl,711':>
t 9.11 l 'l.Oo 19. Hi 18.?I\ tt1 0 R9 19 .11 111.e. 7 19.11 19.11 19. '>0 19.711 19 • Ull I •1. 711 l'l.ol
11.1111 o.719 o. fJl
o.1n
u.101 0.1011 0. e.11'> o.e.112 0.059 ,, .b45 o.blll li.b2l
II.bl 11 0. '> 11
KIA (
l/~llN)
0.241 o.25t. 0.2811 0.100 0.1111 0 0 3b5 0.119 0.105 0.1101 0.1101 0.1112 0.1115 0.1111 0.1135 0.11110 o. 1
O.llbO o.11s11 o.11so 0 0 11b4 0.11011 0.11118 0.455 0.1156 0 0 115'i o. 4'!>8 0.1100 0.1153 1.3b3 l. 3112 1.3S7 1.101 l. 3'!>5 1.1110 1 • .536 1.121 1.110 1.299 1.2n l .Zll l l.213 I • \I\ I 1.1s1 I. Ill 1.0911 1.0119 1.013 o.97o 0.929 o.895 o.1no 0.800 0.759 0.106 o.c.5e. O.b09
JULIAh DATES
395 (LANGLEYS/'4Jl'O
o.ss2 o.a.28 Oob1b 0.121 0.7'.7 o.818 0.8bo o.904 0.9112 o.978 1.021 l.Obb 1.090 1.1211 1.101 l. I 79 1.200 l.ns 1.2110 1.2511 1.21e 1.279 1.291 l.lOI 1.309 1 0 Z9l 1. 301 1. 307 1. 30.S l. 282 1.2714 I• lb1 1.201 1.243 1.2111 1.190 l.lbl 1.128 l.101 1.0111 l.039 1.00.s o.9b7 0.910 0.885 o.852 0.1111 O.H1 o. 721 O.b7Z O.b27. o.578
75111 1111'
(LANIOLEYSl.,J '-1)
o.95t o.971 1.000 1.0111 t.01111 1. 0 711 1.102 1.111 I. lt2 1.120 1.150 1.1911 \ 0 U9 1.209 1.223 1.2111 1.2011 1.218 1.218 l-.2Z3 1.218 I• 2111 1.2Z8 l.U8 1.233 1.2011 1.221 1.238 I .2113 1.223 1.Zll l.2H 1.2116 1.238 l.ZI& 1.199 1.115 1.1111
l.l2b l. lJl 1.101 1.097 1.087 t.Ob8 l.OSA 0.007 1.019 1.0211 1.015 o.9ol 0.932 0 ,90.5
r 0,527
0,0221
111
16'>'>
1 tl,l:l9
o.2n
u,11111;>
l 11
! 705 I 715
l8.b7
0 .11q5 0,111)0 0,3511 o.322 0.2n3 o.2ub to. 1 '>ti 0.112 0.011 0.037
0.199 0 .17':>
o.ot91l 0.0110 0,01118 O.Ol2b 0,0107
111 111 111 111 111
111 111 111 I 11
N VI
U9[PA
t>A Tl
JUL)~\
l! "[
17?5 1735 17 18?".l
11135
T ['11'
l ll, 7P. 111.1''1 18 ,11'1 HJ, lM
IR." 4 1ll. Ob
1 7, 78 lb.22 I 1.1.94
0. 2 .. 7
o.1c;o
0, 12b 0. 111 (1. 085 ll.Ob3 0,045 0.010 0.011 0,007
UV (LANGLEYS/Mlt-4) 0.02115
0,0088
0.0011 0. 005';) 0.0040 0,0026 0.0011
LUNAN 041[;
11-21-1()
0.161 o.HJ 0,282 0,240 0.19b 0 .1119 0 .110 0.(>79
o.04b 0.019
75111 '4IP
(LANGLEYS/MIN) 0.6741
o.835 o. 777 0,726 O.b641 O.b?b 0,576
o.so!> 0 .1111
o.:no
o.2s2 0 .1 ~5
o.o
1'11
Sl1'4LJG11T
JtJLIA~l II
N
°'
i-.' F
111 112 112 112 1I2 112 112 11 (' 1I2 112 112 112 112 11? 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 11 c)
(Pf'h)
(I /l~}N)
CLA"4GLEYS/MIN)
0.011> 0.018
Cf05 CflS Cf('S Clll':J
1.u 1 •I 7 I • 11 1. u1> 1. I 7 1.114 1.12 2. I 7 .s.22 3,911 11.50 5.ol o.'>O 7. b 1 B.12 9,':>b 10.39 10.911 1 I • 1b 11.83 12.bl 13,H I 1015 !025
17. 72 16,0o 1 t\. ':>b 1'1.00 19.oO 19.'lb 19.50 20.11 20.22 20 • .Cll 20.H 21.7b 21.0b 20, 71'> 21.22 21.t> 1 ?l.t>l 22,00
o.t>a11 u.b90 o.1:>Q6 0.100 0.100 o.7ot1 o. lilt\ 0.120 0.120
0.001 0. 001 o.oob 0.010 0.019 0.029 0.039 0. 05tl 0.011 0.093 0 .1111 o. llb u.15b 0.1811 0,20.S o ••n 9 0.231> 0.21>0 0.211 0.295 o.3011 o. 31 ii o.329 0.335 11. 3t11 0. 3'> l 0 0 .H7 0,382 o.l8b 0,389 o.398 o.t100 o. ':>':> 1>05 b I') 1>25 b35
f>,115 t.'>5 70'> 715 7?';,
735 711':> 755 1105 At':> 625 113"> 6115 ~5'>
10.S~
104"> 10'>5 1105 1115 1125 11 J'5
1111"> 1155 12(1'> 121"> 1225
1735 1211s 130'> 131'> 132'> 133'>
n11c; 1355 1 .. os
U,IH
23, 1 I 22. 72 22.nl l.i.l0 o.2b
•l.5'>1> 0.'>70 0.58 0.0075 0 0 00Qll 0.0115 0,013'> O,Ul59 0. 011:\3 0.0208 0.0212 0.0257 0.0279 0.010'> 0.03211 0,0351 O.OHti o.o39c 0.0415 0.011.ss 0.04511 0.0467 o.os11 o.os.B 0.05'>0 o.osbo 0.057'> 0.051111 o.Ob16 O,Ool2 0 0 01>111 o.Ob59 O.Obbl O.Ub73 o.Ob75 0.0008 0 0 0b10 o.ob70 0 0 0bbb 0 0 0050 ei.01>27 0.01>25 0.0011 0.0001 0.0'>87 0.0571 0.0558
LUNAR DATE:
11-22-75
TSR (LA!l1GLE'l'S/'4lN)
o.o o.o 0.009 0.022 o.o:s2 0.0119 0.110 0. 14111 0.116 0.211 0.2'>1> o.292 o.311b 0. ll'IJ o.510 o.Scl 0. 51\1 o.57 1.105 1,138 I .15Cl 1. 1 t:l I 1.198 l, 237 l.25b 1.2t>7 I. 288 J ,286 1.101 l.3011 1.297 1.2 1n 1.299 1.291) 1.211 1.239 1.232 1.209 I .1911 I.lob I • 1411 1.121
JULI AN DA TE:
39';> (LANGl.EYS/MJN)
o.o 0.001 0.012 0.021 O.Olb 0.052 O.llb 0.11>0 0.20.s o.246 0.2911 0,3311 o.361 0 .1134 0.1179 o.52'> o.57~
o.t.i.s a.bbl II• 1 Otl
0.1119 0.791 O.BH 0.8b9 0,901 0,942 1.001 1. 040 1,on I. 1 0 I 1.119 l.1.S9 1 • I'> 11 1.190 l,20b 1.218 l.23b l. ?3b 1.2 lllt'S l tJ35 lll115 Ill'>':> 1s;o5 151"> 152'> 1':>115 1555 lt-O'> lbl'i lb?5 lb3'> lt-«5
23 • .B ?.3 .o I 23.B iJ • .?6 23.72 23,'>b 23.50
Uoblo O.b7tl 0.07.? 0.002 OobllO
o.:s15 o. 377
2 3 .11.s 2.s,1n
I).
23.11 2 J..b 7 23.o7 2.S,72 2.S.ll3 23.72 2.S.'>b 23.t>l 23.211 23.17 23,26
0 .11112 0.'>'111 o. 5311 \) .518 0.1115 ll'OS
1111"'
22.8.S
n. 7t'
21. Q4 21 ,Ob
I 8
112
111~5
I q .1111 111,b 7 17.911
O.blB
0,b211 bl.? o.Sdll
I(! A
0 • .511
O.loO o.338 o.33b 0.121 o.312 0 0 o
0.011 0.0011 0.001
fl:O.
b/1•0
Ull CLA"'GLEYS/Ml .10
o. o5:s11 0.0517 o.osoo 0.01178 O.OQ53 o.011H 0.01109 o.03bl 0.01111 0.0220 0.02115 0.0210
o.02s1 o.o2lb 0.0193 o.Ol 73 0.011111 o.01t9 0.0110
o.oo•H
0.0015 0.00513 0.001111 0.0011 11.00~0
0.0011 0.00011 0.0001
LUNAR 041£.:
11-22•75
TSR (lAlllGLEYS/MlNl
l.08b 1.002 1.037 o.'18'> 0.911b o. 1HO 0 0 1\b'I 0 • tllO o. 751 0 .2?11 o.t>92 0.111:12 o.bll 0.1199 0 .11117 0 .11011 0.11111 o.299 o.258 0.211 O.lbb
.JULIAN DATE:
l'I'> (LANGLEYS/MIN)
l.OH 1. 0 I U o.'185 o.'lllO o.901 o.ll&b 0.828 o.79.S o. 713 0.2011 O.bbl o. blll\ 0 • ., 7 'l o.11n 0.1125 o • .S8'> 0.32tl o. 21111 0.211.s 0.199
75112
llllP (LANGLEYS/Ml'll
1.058 1.0311 l. 02'1 1.010 o.995 0.9115 O.'lbb
0.951 o.e'IJ 0.02'1 o.835 o.&Ob 0.1101 o. 7H 0.109 ri. b811 o.t>2o
o.s1n
o.oH
o.1s~
0,539 0.117b 0.1101
0.013
0,0bB
o.oa? 0.0111 0.0211 o.ooq
0,078 0.0'>1 0.010 o.ooq
o. 0
o.o
0,236 0 .1 so 0 0 0b8 o.o o.o o.o
o.o
o.o
'
r
rll l
5tl'ILJf,lq
Jt1L J A,,
IE ST)
113 11 3 113 113 113 113
1200 1205 1?15
lU lU 11 l
113 11.S 113 113 113 113 1 ll Jll 113 113 l 13 00
l} ·Vt
uA I (
I I3
l'V
I :.r l '• S l T t S ltJ!J V:
113 113 11.s 113 113 113 113 113 113 113 113 11 3 113 113 113 113 113 11.S 113 115 113 11 l 113 11 3
lB 113 113 11 l 113 I 1~ 113
I i'2v 1225 1230 1235 12ll0 124'> 12'>0 1?55 1300 1305 1310 1315 1320 1325 1330 1335 lltiO 1311'> 1350 1l55 1 q Otl llJ05 1ti10 11115 11120 142':> 1430
rt ·~r ("CJ
24.1/ 23.1>7 ?3. 9.-llJ 25.22 211.12 24.ll'I 25.U 25.21\ 25,1111 25.51> 25.n 21l.83 25.50 25.H ?5.H 25. I ti':>O 11155 J 500 1505 I'> I u
1'>15 152u 152'i 15 \(I I '53'5 I C,110 1c;11r;;, l':.':>0
16115 I t-1 ll Jn 15 I 020
9 0.106 0.201 o.25'1 o • .?13 0.2113 0.210 0.120 0 • .S111 0 • 31JO 0 0 2R8 0.212 o.314 0,203 o.29'1 0.110 o.297 O,i'1!3 0.220 O• 20 I 0.209 0. 111\
0.1'15 0.115
0,026H
0,0162 0.01115 0.01123 0,04211 0.03911 0,01102 0.01101 0.011111 O.Olb3 0.03811 0.0321.1 0,0523 0.0155 O.OllOb 0.0111>1
'l.047ti 0 0 03411 o.011ou 0 • O">c!O o.os11 0.03b3 0.0135 0.0122 0.01111 0.03116 0,01153. 0.01110 0.01103 0.0297 0.0105 0.0322 0.0100 0.0389 0.03 1 •.HO 1.009 0.0116 0,5ol 0,1180 O,b32 o.57o o.753 0,759 O,o52 0.112 0,703 O.bb2 o.508 o.58'1 o.505 1.0b7 o.589 0.7H o.925 i.0211 o.5112 o.5911 I • l 1111 1.oao O.bo2 0 0 5A1 o.5311 0,5711 0.111 0.925 0 0 llH 1.020 o • .S40 0.11111 0 .1115 0.11111 0 0 A73 o.832 0.1190 ll 0 !1b5 0 0 b30 o.329 0.11110 0.301 0 .1111 0,51>3
JULIAN DATE:
HS (LANGLlYS/"IJN)
I. 23 I
0.576 O.SbO 0.557 0.890 l.252 O.'lbl O,b52 0,':>30 0,1152 0,599 0,5110 o.11s 0.1211 o. bl ti 0 0 07'1 0.009 o.nll o.s.n o.558 0.117b
1.018 o.soo 0 0 t>9o 0. 81111 0,97b o.515 0.557 1.068 1. 031 O.b27 0,5')1 o.5u11 o .5t1 ! o.o9l 0.1!75 0 .1115 O,ll]l 0.111 0.111 q 0.387 o.318 0,625 o.788 0.8115 0,819 o.597 0.309 0.1157 o.262 0.1143 o.s:s1
75113
'HP (LA"'GLf.'fS/"4JN)
0.070 0.010 0,0 o.03 0.139 0.1011 o.o9t> 11. 0115 0.0111 O.Obb o.ob5 0.004 o.o5c o. vll8 0.0115 0.019 0.0111 0.010 0.024 0.010 0.015 0,009 0,008 o.uoo 0.002
11>40 lbCI 1710 171 '> 1120 172'> 1nn 173'> l 7llv 1711'"> J 75fl
17':>'> 1110•) 11105 1810 11'15 11120 1825
~4.t>7
2u.72 ?4.7!\ 2.;. 7 t< 24.7? 2'I 23.5b 23.H
21.n c:'.S. I I
22.119 22.U 22.bl ~2.ol
113
11135
113
J l'Qll
22.H 22.2s 22.3j
113
1110s
22.0b
J l\Jfl
0.178 II
0
10:,9
0. I 8 U'V (LU.GLEYS/Ml'O
0.01 u 0.0211 O.Oc?l l
0.0193 0.0168 o.Olbb 0 0 011l2 0.0128 0.0101 o.oo9b o.001H 0.0082 0. 001'1
o.ooso 0.0011 0.0002 O.OO';>b 0.0050 0.00115 0.0039 0.002.., 0.002.s 0.0019 0.0015 0.0011 0.0001 0.0004
LllNAR DAll:
ll-23-75
TSR (LA"GLfYS/'41Nl
o.348 O.bll o.305 O.llb9 o.237 0.1110 o.157 0. 325 0 0 2';,R o. t 7b 0 .172
0.118 0.1112 o.151 0.127 0.105 0.090 0.0112 0.!>75 0 0 0&2 0 0 0ll.! o.o.so 0.02& 0.022
o. 0 IS o.OOb o.o
JULIAN DATE:
3q5 (LAlllGLEYSl'41N)
0.331 o.su o.265 0.43b 0.219 o.199
o.:no
0.299 0.2H 0.1011 0. l 58 0.112 0.133 0.1112 0.119 0.101 0.087 0.079 0.01.s O.Obl o. 04.S 0.030 0.021 0.021 O.Olb 0.009 0.003
751 l l °"JP
(LAN:iLEYS/'41~)
0.131
o.Ssl
0.1)211 0.592 0.053 O.b01 o.s1s 0.115b 0.1115 0 .112 0.110
o.o
0.0211 0 0 0bl
0.01111 0.010 o.o o.o o.o o.o
o.o
o.o o.o o.o o.o (). 0 o.o
1·
_., ~
"
J
~ "1 J S.J•"L l (,n r J>,lf'
75115
~
Jdl I
ll•'l
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JULIAN DATE:
395 (LANGlEYS1"4lN)
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75283 ~IP
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o.02u o.797 0.889 O,IH5 o.559 0,2H O,blll 0.029 0.015 0,019 0.015 0 0 097 0.8115 0.029 0.015 0.105 0,029 0.092 0.015 0.0111 0,015 0,015 0.029 I). 0214 I). 0 311
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JULIAN OAIE;
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