Ultraviolet-absorption photometer for

measurement of ozone on a rocket-boosted

payload

B. Sen, W. R. Sheldon, and J. R. Benbrook

We developed a rocket payload to perform in situ measurements of atmospheric ozone at the University
of Houston. The ozone detector is a dual-beam UV-absorption photometer that uses the 253.7-nm
radiation from a low-pressure mercury-vapor lamp to illuminate two identical absorption chambers. We
describe the design features and the operation of the instrument. The fundamental resolution of the
photometer is shown to be 2.7 � 1015 molecules m�3. We present the ozone profile measured during
parachute descent following boosted ascent to 60 km by a Nike–Orion rocket. The uncertainty in the
measurement of this ozone profile is estimated to be 8.2%. © 1996 Optical Society of America
Key words: UV-absorption photometer, rocket instrument, stratospheric ozone.

1. Introduction can determine the ozone concentration by measuring

Ozone �O3� is a vital constituent of the middle and
lower atmosphere, even though it is present in only
trace quantities. Almost all solar UV radiation with
wavelengths �320 nm is absorbed by ozone in the
stratosphere �12–55 km�, thus providing protection
from this biologically harmful radiation. Also, the
absorption of infrared radiation from the Earth’s sur-
face by ozone plays an important role in the global
temperature balance. As a consequence of its im-
portance to conditions at the Earth’s surface, global
ozone monitoring has been conducted continuously
for a number of decades.1
The total column density of ozone has been moni-
tored by both ground-based instruments and detec-
tors on Earth-orbiting satellites. High-resolution
altitude profiles of atmospheric ozone have been mea-
sured in situ by balloon-2,3 and aircraft-borne instru-
ments.4
The UV-absorption technique has been used exten-
sively to make in situ ozone measurements.5 One
When this research was performed the authors were with the
Department of Physics, University of Houston, 4800 Calhoun
Road, Houston, Texas 77204-5506. B. Sen is now with the Jet
Propulsion Laboratory, 4800 Oak Grove Drive, Pasadena, Califor-
nia 91109-8099.
Received 16 October 1995; revised manuscript received 10 June
1996.
0003-6935�96�306010-05$10.00�0
© 1996 Optical Society of America
the transmittance at 253.7 nm in an air sample that
flows through a chamber. Because the absorption
cross section of ozone at this wavelength has been
accurately measured,6 the UV-absorption photome-
ter can make an absolute determination of the ozone
concentration, which is a major advantage over other
techniques.
We describe the design, construction, and flight
performance of the University of Houston �UH� dual-
chamber UV-absorption photometer. The design
uses two folded 1.122-m columns as the absorption
chambers and UV-sensitive solid-state photodiodes
as light detectors to accomplish high-sensitivity
ozone absorption measurements. The UV-absorption
photometer was designed as the primary instrument
of a rocket-boosted payload. The payload was test
flown at the Wallops Island Flight Facility, Virginia,
in August 1992.
2. UV-Absorption Photometer
Ozone measurement with the photometer technique
is based on straightforward principles of physics.
The relationship between the light intensity mea-
sured by a photometer instrument and the concen-
tration of ozone in an absorption chamber is derived
from the Beer–Bouguer–Lambert law for the absorp-
tion of radiation7:
I � I0 exp����O3�cL� (1)

6010 APPLIED OPTICS � Vol. 35, No. 30 � 20 October 1996


Fig. 1. Block diagram of the UH dual-column UV-absorption pho-
tometer.
or
�O3�c �
1
�L
loge
I
��
I0
, (2)
where I is the 253.7-nm intensity after attenuation by
ambient ozone in the absorption chamber, I0 is the
same measurement with ozone removed by the chem-
ical action of a scrubber, L is the path length of the
absorption chamber, � is the molecular-absorption
cross section of ozone at 253.7 nm, and �O3�c is the
mean molecular concentration of ozone in the absorp-
tion chamber when I is measured. The chamber
ozone concentration �O3�c and the ambient ozone den-
sity �O3�amb are related by the expression
PcTamb
�O3�amb � �O3�c , (3)
TcPamb
where Pamb, Pc, Tamb, and Tc are the ambient and
chamber pressures and temperatures. The ozone
volume mixing ratio f�O3�amb is expressed as
�O3�amb kTc
f�O3�amb � � �O3�c , (4)
�M� Pc
where k is the Boltzmann constant and �M� is the
ambient air density.
Described in detail in Ref. 8, the UH dual-chamber
UV-absorption instrument is illustrated in Fig. 1. It
is an outgrowth of an instrument developed by Rob-
bins9 and is similar to one assembled at NOAA.5
The photometer has three basic components: the
two absorption chambers with a pump and valve, the
UV light source for the 253.7-nm radiation and asso-
ciated optics, and the solid-state detectors and elec-
tronics. As illustrated in Fig. 1, the lamp output is
directed down the length of the folded absorption
chamber to the detectors. Ozone partially absorbs
the radiation at 253.7 nm so that changes in the
molecular concentration of ozone in the chamber pro-
duce changes in the light intensity measured by the
detectors. With the use of a chemical scrubber �cop-
per screens impregnated with magnesium dioxide
and metallic copper and passivated at 800 °C� to pro-
duce ozone-free air and a four-port valve to alternate
this scrubbed air between the two chambers, one can
take measurements of ozone concentration for each
chamber in one cycle of the valve.
The absorption chambers are made from four alu-
minum tubes of 0.457-m length each. Two tubes
held between the mirror and lamp blocks, as shown in
Fig. 1, make each of the two 1.122-m path lengths.
The chambers are held in the blocks using aluminum
face plates and O rings compressed around the tube
ends. We used coated mirrors to maximize their UV
reflectance and aligned them so that the lamp illu-
minates the detectors at the end of each absorption
chamber. We mounted the lamp and the photo-
diodes using similar techniques �aluminum face
plates and O rings� to provide ease of assembly and
structural rigidity. This configuration allows quick
disassembly of the absorption chambers, lamp, and
mirror systems for cleaning and replacement. We
coated all the metal surfaces in direct contact with
the air samples with polytetrafluoroethylene �Du-
Pont Teflon� to minimize wall losses of ozone in the
photometer.
The light source for the UH photometer is a low-
pressure mercury-vapor lamp driven by a 5-kHz,
800-V �peak� square wave. Potentially, there is a
problem when a mercury-vapor lamp is used for this
purpose because mercury has an emission line at 185
nm that is capable of dissociating O2 and thus creat-
ing O3 within the instrument. However, the lamp
has a special quartz jacket to block the 185-nm emis-
sion line; it emits approximately 80% of its radiant
energy at 253.7 nm. For measurement of the
253.7-nm light, the UH instrument uses three silicon
photodiodes, one at the end of each absorption cham-
ber and one immediately adjacent to the lamp as a
monitor. The solid-state detectors have high sensi-
tivity in the UV at the expense of reduced perfor-
mance in the long-wavelength region. This reduced
sensitivity at longer wavelengths results in less ther-
mal noise. Although the peak efficiency of the pho-
todiodes occurs at 720 nm, where they are four times
more sensitive than at 253.7 nm, the use of narrow-
band UV filters ensures that all photometric mea-
surements are made at 253.7 nm. The narrow-band
UV filter has a peak transmission of approximately
18% at 253.7 nm, a bandwidth of 10 nm at half-
intensity and less than 0.01% transmission outside
the passband; the resulting ratio of UV signal to
background noise contributes significantly to the
quality of the photometer measurements. One of
these narrow-band UV filters is located at the en-
trance aperture of each photodiode.
20 October 1996 � Vol. 35, No. 30 � APPLIED OPTICS 6011
 The weak UV intensity at the chamber end results
in a very small current ��7 nA� at the photodiode
outputs. Consequently, signal-to-noise performance
is an important design consideration for the photom-
eter electronics. The preamplifier is a precision
transconductance amplifier with field-effect transis-
tor inputs. The drift current in this amplifier ��3
pA� is far less than the nominal photodiode output, so
the total noise is dominated by the signal-to-noise
performance of the solid-state detectors �see Ref. 8,
Appendix 1�. The outputs of the current-to-voltage
converters are amplified further by a factor of 10,
inverted, and fed to voltage-to-frequency converters.
The linear converters produce a 1-MHz output for an
input signal of 10 V.
The electronics system of the ozone payload is de-
signed around the Motorola 68000 microprocessor.
Three sets of 24-bit scalers connected to the micro-
processor bus were used to count the pulses produced
by the voltage-to-frequency converters. We used a
precision time-delay unit controlled by the micropro-
cessor to produce the time intervals that constitute a
measurement cycle for the instrument. The time-
delay unit consists of a presettable 8-bit scaler that is
driven by a prescaled input signal. Overflow of the
8-bit scaler signals the end of the delay period. The
control word sent to the time-delay unit by the mi-
croprocessor consists of 8 bits to preset the counter
and 3 bits to select one of eight prescaler channels.
The input signal to the prescaler is selected by the
microprocessor to be either the 10-MHz crystal clock
that drives the microprocessor or the output of the
voltage-to-frequency converter driven by the lamp
monitor. The eight prescaler channels cover the
range from divide-by-2 to divide-by-214, so a very
wide range of possible measurement time intervals is
available for the instrument.
The computer algorithm in the photometer pro-
duces a measurement cycle that is composed of three
segments: �1� absorption chamber flush delay, �2�
frequency measurement, and �3� ozone measure-
ment. For the flush delay and frequency measure-
ment segments, the input to the time-delay unit is the
10-MHz clock signal. We used the computer to se-
lect one of five delay times ranging from 1 to 15 s
under the control of an up-link telemetry command.
After the flush delay is complete, we initiated a 1-s
delay during which the three sets of scalers accumu-
late the counts from the three voltage-to-frequency
converters. These counts are telemetered as part of
the 64-word data frame so that the frequencies of the
three oscillators can be monitored. After the com-
pletion of the frequency measurement, the input to
the time-delay unit is changed to the lamp monitor
output and a delay interval corresponding to 290,816
counts from the monitor is begun. The counts from
the two chambers accumulated during this period are
then used to compute the ozone concentration in each
channel. Because the same number of lamp monitor
counts are accumulated on successive cycles of mea-
surement, the integrated light intensity is expected
to be the same if the drift rate of the monitor oscilla-
6012 APPLIED OPTICS � Vol. 35, No. 30 � 20 October 1996
tor is small. In practice, all three oscillators drift
slowly, but their relative rates of change are approx-
imately equal. The algorithm used to compute the
ozone concentration actually uses the counts from the
two previous measurement cycles to do a first-order
linear correction to remove drifts. Thus the result is
that the telemetered ozone values are actually for the
preceding measurement cycle rather than for the one
just completed. At the end of the ozone measure-
ment cycle the four-port valve is switched to alternate
the gas mode �ambient air or scrubbed air� in each
absorption chamber.
The frequency measurements can also be used to
calculate the ozone concentration after suitable nor-
malization corrections. If this determination of �O3�
were significantly different from that obtained during
the ozone measurement cycle, it would indicate that
the flush time is probably set too low. The up-link
command unit allows the cycle to be adjusted to the
shortest interval that will produce reliable results so
that the maximum measurement rate can be main-
tained as the parachuted payload descends through
the upper regions of interest. Laboratory tests indi-
cate that the columns flush to the 90% level in less
than 1 s at sea level. Comparison of the �O3� com-
puted from the frequency cycle and the measurement
cycle for the test flight discussed below indicate that
the 1-s flush time is adequate for altitudes to at least
40 km.
Photometer engineering information �such as volt-
ages, currents, temperatures, and pressures� are dig-
itized by an analog-to-digital converter circuit that is
connected to the microprocessor data bus. The
pulsed-code modulation data that are sent to the te-
lemetry system were generated by the microproces-
sor and then telemetered on a single subcarrier
�adequate to handle the 9.77-kbit s�1 data rate�.
The signal is stored and decoded at the ground sta-
tion for real-time display of ozone measurements and
photometer operation status.
The path length in the UH photometer’s absorption
chamber L is 1.122 � 0.005 m, and the accepted value
of � for ozone at 253.7 nm is 1.14 � 10�21 m2 mole-
cules�1 �see Ref. 6�. With a counting error of �1 in
the digital circuitry computing the measurement �I0
� I� and a maximum count I0 of 290,816 counts, we
obtained the theoretical instrumental resolution of
the photometer as 2.7 � 1015 molecules m�3 �or
�0.07% at 26 km, the peak in the mid-latitude ozone
distribution; �12% at 55 km, the maximum measure-
ment height of the UH photometer on its maiden
rocket-boosted flight�.
Experimentally, the statistical uncertainty in the
measured counts is much larger than �1. To deter-
mine the uncertainty in ozone measurements made
by the UH dual-chamber UV-absorption photometer,
we calculated the standard deviations about the
mean of laboratory measurements for a wide range of
ozone concentrations. The standard deviation in the
measurement of ozone concentration increased from
3.1 � 1016 molecules m�3 for scrubbed ambient air to
3.9 � 1016 molecules m�3 for an ozone concentration
of approximately 9 � 1018 molecules m�3.
3. Results and Discussion
The engineering test flight of the rocket-boosted UH
UV-absorption photometer was conducted on 21 Au-
gust 1992. The vertical profile of atmospheric ozone
concentration was measured during parachute de-
scent by the photometer following launch from the
Wallops Island Flight Facility, Virginia �38 °N,
75 °W�, an area of typical mid-latitude ozone distri-
bution. Measurements obtained during this flight
provided details that have been used to modify and
improve the UH dual-chamber UV-absorption pho-
tometer.
The payload reached a maximum altitude of 82 km
��0.008 hPa� prior to parachute deployment and de-
scent. The photometer was powered on prior to
rocket launch and an onboard countdown timer
Fig. 2. Profile of ozone volume mixing ratio measured by the
maintained the instrument in a sleep state for safety
rocket-boosted photometer during a 1-h parachute descent. Mea-
reasons. Ozone measurements commenced on sep- surement was made over Wallops Island Flight Facility, Virginia,
aration of the payload from the launch vehicle and �38 °N, 75 °W�.
continued to as low as 4 km. The photometer was
switched off prior to an air-snatch recovery of payload
and parachute.
Postflight examination of the payload revealed the and losses within the photometer. The length of the
complete destruction of the ambient-air temperature absorption chamber L is known to a high degree of
probes. The engineering data indicated that the accuracy. Although the absolute cross section � at
very high acceleration imparted to the photometer 253.7 nm is also well known, its dependence on tem-
during separation from the rocket at apoapsis was perature and pressure is a source of error. However,
the probable cause. Coupled with an unfortunate the largest contributors to measurement error during
electronic mishap that caused loss of radar lock, the the engineering flight of the payload were noise in the
altitude of the payload could be determined only be- lamp–photodiode system, wall losses, and lack of data
low 55 km. on ambient pressure and temperature.
To determine the ambient ozone concentration The measurement of ambient pressure and tem-
�O3�amb from the measurements made by the UV- perature is a large source of error only in the engi-
absorption photometer, a climatological temperature neering flight of the UV-absorption photometer. An
profile based on CIRA10 was used from ground to 0.2 appropriate choice of pressure and temperature sen-
hPa ��60 km�. From previous experience, the dif- sors for reliable performance under flight conditions
ference in the climatological and measured tempera- have since rectified this source of error. Prior expe-
ture can be as large as 10 K and constitutes a source rience with these temperature and pressure sensors8
of error of 5%; however, the ozone volume mixing have allowed measurements to be made with signif-
ratio �VMR� does not require accurate measurements icantly better accuracy �3%�.
of ambient pressures and temperatures. Figure 2 Loss of ozone to the walls of the photometer is
illustrates the VMR profile obtained by the UV- probably the largest source of error during measure-
absorption photometer during parachute descent. ments made at altitudes of 40 km or higher. As
The profile was acquired with the measurement cycle previously stated, the UH UV-absorption photometer
set at 4 s. The ozone VMR reached a peak value of walls were coated with polytetrafluroethylene to min-
7 parts in 106 by volume at approximately 30 km. imize such losses. Ozone measurements made with
The figure also demonstrates the high vertical reso- balloon-borne UV photometers3,5,11 indicate negligi-
lution achieved by the UH UV-absorption photometer ble loss below 22 km and �5% below 40 km. The
in capturing the sharp, narrow structures in the level of agreement between simultaneous balloon-
ozone profile in the lower stratosphere and tropo-
sphere. These structures in the ozone VMR profile
have been observed and discussed for other in situ Table 1. UH UV-Photometer Accuracy
detectors5 and are not noise in the UH UV photom- Contributor Estimated %
eter measurements.
The sources of error that limit the overall accuracy Lamp and photodiode 4
of the UH UV-absorption photometer are summa- � and L 1
rized in Table 1. The main contribution to the ab- P and T 5–8
Absolute accuracy 8.2
solute accuracy arises from the uncertainty in the
Wall loss 2–20
chamber length, the absorption cross section of ozone,

20 October 1996 � Vol. 35, No. 30 � APPLIED OPTICS 6013

borne measurements of ozone profiles below 32 km in
the Arctic12 and below 40 km at mid-latitudes by the
UH photometers and Centre National de la Re-
cherche Scientifique, Service d’Aéronomie chemilu-
minescence detector also indicate that wall losses in
the UH instrument are �5%. However, measure-
ments have not established the extent of ozone losses
on surfaces at the higher altitudes traversed by the
rocket-boosted payload. Estimates from model and
laboratory simulations provide the 2–20% value pre-
sented in Table 1.
We used the UH dual-chamber UV-absorption pho-
tometer to demonstrate that a laboratory-quality,
high-sensitivity instrument can be operated in ad-
verse field environments. The rapid response time
makes the UH photometer an ideal detector for the
determination of detailed vertical profiles of atmo-
spheric ozone—measurements that are of particular
importance in stratospheric chemistry.
The research we described in this paper was pre-
sented to the University of Houston as a part of a
Doctor of Philosophy dissertation.8 This research
was partially supported by NASA grant NAG9-213
and by the Texas Advanced Research Program.
Field operations at the Wallops Island Flight Facility
were supported by NASA headquarters and by the
UH Institute for Space System Operations. Partial
support for the data analysis was provided by the
U.S. Air Force.
References
1. World Meteorological Organisation, Scientific Assessment of
Ozone Depletion: 1991, Report 25 �World Meteorological Or-
ganisation, 1991�.
2. P. Aimedieu, A. J. Krueger, D. E. Robbins, and P. C. Simon,
“Ozone profile intercomparison based on simultaneous obser-
6014 APPLIED OPTICS � Vol. 35, No. 30 � 20 October 1996
vations between 20 and 40 km,” Planet. Space Sci. 31, 801– 807
�1983�.
3. E. Hilsenrath, W. Attmannspacher, A. Bass, W. Evans, R.
Hagemeyer, R. A. Barnes, W. Komhyr, K. Mauersberger, J.
Mentall, M. Proffitt, D. Robbins, S. Taylor, A. Torres, and E.
Weinstock, “Results from the Balloon Ozone Intercomparison
Campaign �BOIC�,” J. Geophys. Res. 91, 3137–3152 �1986�.
4. M. H. Proffitt, M. J. Steinkamp, J. A. Powell, R. J. McLaughlin,
O. A. Mills, A. L. Schmeltekopf, T. L. Thompson, A. F. Tuck, T.
Tyler, R. H. Winkler, and K. R. Chan, “In-situ ozone measure-
ments within the 1987 Antarctic ozone hole from a high-altitude
ER-2 aircraft,” J. Geophys. Res. 94, 16547–16555 �1989�.
5. M. H. Proffitt and R. J. McLaughlin, “Fast response dual beam
UV absorption photometer for use on stratospheric balloons,”
Rev. Sci. Instrum. 54, 1719 –1728 �1983�.
6. W. B. DeMore, S. P. Sander, D. M. Golden, C. J. Howard, A. R.
Ravishankara, C. E. Kolb, and M. J. Molina, Chemical Kinetics
and Photochemical Data for use in Stratospheric Modelling
JPL pub. 94-26 �Jet Propulsion Laboratory, Pasadena, Calif.,
1994�.
7. F. C. Strong, “Theoretical basis of Bouguer-Beer law of radia-
tion absorption,” Anal. Chem. 24, 338 –340 �1952�.
8. B. Sen, “Development of ultraviolet absorption photometer for
atmospheric ozone measurement and results from mid-
latitude investigations,” Ph.D. dissertation �University of
Houston, Houston, Texas, 1992�.
9. D. E. Robbins, “NASA-JSC measurements during ’la Cam-
paigne d’Intercomparison d’Ozonometres’, Gap, France, June
1981,” Planet. Space Sci. 31, 761–765 �1983�.
10. CIRA, COSPAR International Reference Atmosphere �Akad-
emie, Berlin, 1972�.
11. J. E. Ainsworth, J. R. Hagemeyer, and E. I. Reed, “Error in
Dasibi flight measurements of atmospheric ozone due to in-
strument wall-loss,” Geophys. Res. Lett. 8, 1071–1074 �1981�.
12. D. J. Hofmann, T. L. Deshler, P. Aimedieu, W. A. Matthews,
P. V. Johnston, Y. Kondo, W. R. Sheldon, G. J. Byrne, and J. R.
Benbrook, “Stratospheric clouds and ozone depletion in Arctic
during January 1989,” Nature �London� 340, 117–121 �1989�.