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MAX-DOAS observations from

ground, ship, and research aircraft:
maximizing signal-to-noise to
measure 'weak' absorbers

Rainer Volkamer, Sean Coburn, Barbara Dix, Roman

Sinreich

Rainer Volkamer, Sean Coburn, Barbara Dix, Roman Sinreich, "MAX-DOAS

observations from ground, ship, and research aircraft: maximizing signal-to-
noise to measure 'weak' absorbers," Proc. SPIE 7462, Ultraviolet and Visible
Ground- and Space-based Measurements, Trace Gases, Aerosols and Effects
VI, 746203 (26 August 2009); doi: 10.1117/12.826792

Event: SPIE Optical Engineering + Applications, 2009, San Diego, California,

United States

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 MAX-DOAS observations from ground, ship, and research aircraft:
maximizing signal-to-noise to measure ‘weak’ absorbers
Rainer Volkamer*ab, Sean Coburna, Barbara Dixa, Roman Sinreicha
a
Dept. of Chemistry and Biochemistry, University of Colorado, UCB 215, Boulder, CO USA 80309
b
Cooperative Institute for Research in the Environmental Studies (CIRES), University of Colorado,
UCB 215, Boulder, CO USA 80309

ABSTRACT

Multi AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) instruments, as solar straylight satellites,
require an accurate characterization and elimination of Fraunhofer lines from solar straylight spectra to measure the
atmospheric column abundance of reactive gases that destroy toxic and heat trapping ozone and form climate cooling
aerosols, like glyoxal (CHOCHO), iodine oxide (IO), or bromine oxide (BrO). The currently achievable noise levels
with state-of-the-art DOAS instruments are limited to δ’DL ≈ 10-4 (noise equivalent differential optical density, δ’);
further noise reductions are typically not straightforward, and the reason for this barrier is not well understood. Here we
demonstrate that the nonlinearity of state-of-the-art CCD detectors poses a limitation to accurately characterize
Fraunhofer lines; the incomplete elimination of Fraunhofer lines is found to cause residual structures of δ’ ≈ 10-4, and
only partially accounted by fitting of an “offset” spectrum. We have developed a novel software tool, the CU Data
Acquisition Code that overcomes this barrier by actively controlling the CCD saturation level, and demonstrates that
δ’DL on the order of 10-5 are possible without apparent limitations from the presence of Fraunhofer lines. The software
also implements active control of the elevation angle (angle with respect to the horizon) by means of a Motion
Compensation System for use with mobile MAX-DOAS deployments from ships and aircraft. Finally, a novel approach
to convert slant column densities into line-of-sight averaged concentrations is discussed.
Keywords: DAC software, CCD, nonlinearity, solar straylight, radiative transfer, O4, IO, glyoxal, MAX-DOAS, motion
compensation, mobile platforms

1. INTRODUCTION
Fraunhofer lines are caused by light absorption of chemical elements (primarily H, Fe, Ni, Ca, Mg, Na) present in the
upper layers of the solar atmosphere. There are thousands of Fraunhofer lines tabulated in the ultraviolet, visible and near
infrared spectral ranges; these lines are superposed as “dark” areas to the thermal back body radiation of the sun. The
elimination of Fraunhofer lines poses experimental challenges if solar photons are used to measure Earth atmospheric
composition of trace gases.1-2 First, Raman scattering leads to the partial “filling-in” of these lines (the “Ring effect”).3
Second, the spectral features of an atmospheric absorber gas measured using “structured” sunlight is different from that
of the same gas measured in the laboratory using a broadband light source (“solar I0“ effect).2,4 Third, for measurements
at moderately low resolution (0.5nm FWHM) the apparent optical depth of Fraunhofer lines is 2-3 orders of magnitude
larger than the optical density of reactive atmospheric trace gases that are of interest to atmospheric chemistry research.
The accurate characterization of Fraunhofer lines is a prerequisite to measure atmospheric trace gases by means of
Differential Optical Absorption Spectroscopy (DOAS).5 DOAS measures atmospheric trace gases by use of their specific
narrow band (<5 nm) ultraviolet–visible light absorption structure in the open atmosphere, separating trace gas
absorption from broadband molecule and aerosol extinction. Nowadays, DOAS is being used from ground, mobile
laboratories, ships, aircraft, and satellite platforms, and can be considered as a reference technique for measurements of
trace gases like bromine oxide (BrO), iodine oxide (IO), chlorine dioxide (OClO), iodine dioxide (OIO), nitrogen dioxide
(NO2), formaldehyde (HCHO), and glyoxal (CHOCHO).1,6-9 Multi AXis DOAS (MAX-DOAS) observes scattered
sunlight under different viewing directions, enabling relatively portable instruments for the spectroscopic remote sensing
of atmospheric trace-gases even if trace layers travel decoupled from ground.10 Furthermore, parameters like the aerosol
extinction coefficient can be derived by (1) measuring trace gases with a known spatial distribution, like the oxygen
dimer O4,11-13 (2) quantitative retrievals of the Ring effect,14 and (3) by intensity ratios at different wavelengths.11

Ultraviolet and Visible Ground- and Space-based Measurements, Trace Gases, Aerosols and Effects VI,
edited by Jay R. Herman, Wei Gao, Proc. of SPIE Vol. 7462, 746203 · © 2009 SPIE
CCC code: 0277-786X/09/$18 · doi: 10.1117/12.826792

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 Fig. 1. Schematic sketch of Ship MAX
X-DOAS (SMAX-DOAS, left) and Airborne MAX-DOAS (AMA
AX-DOAS, right).
Fig. 1. Illustrates how the signal to nooise ratio of mobile MAX-DOAS measurements can be b maximized by
increasing the overlap between photon paaths and an absorber layer. Further, improvements depen
nd on lowering the
instrument noise.
ng Noise
1.1 Current limitations with minimizin
MAX-DOAS and satellite measurementss in the ultraviolet and visible spectral ranges are typically photon-shot noise
limited. The differential optical density, δ’, equivalent to the 2-sigma RMS noise of the residual structure that remains
after known absorbers are removed by m means of numerical least squares fitting (detection limit, δ’DL), scales in good
approximation inversely proportional to tthe number of sampled photons, N (i.e., δ’DL ≈ 2 N-0.5). In
n practice, increasing N
only reduces δ’DL down to about δ’ ≥ 2x10-4.14,15 Further improvements in the detection limit l prove not to be
straightforward. In particular, summing oof multiple spectra to accumulate N > 108 photons typiccally does not result in
noise improvements beyond this thresholdd. Such deviations from photon counting statistics limit th he detection sensitivity
of currently available DOAS instrumentss, including the satellite instruments GOME, SCIAMACH HY, OMI, and GOME-
2. The reasons for this barrier are presenntly not well understood, but the existence of a barrier does not appear to be
limited to a particular spectral range.
munity is to minimize residuals from the following modifieed fitting equation:
A common approach in the DOAS comm

ffset (λ )) = log( I 0 (λ ) − DC − straylight (λ )) − ∑ σ i ci − P (1)

log( I (λ ) − DC − straylight (λ ) − off
where I(λ) is the intensity of the measured spectrum corrected for any electronic offset, DC(λ) is dark
d current, straylight
is instrument straylight, offset(λ) resembbles residual intensity from imperfect corrections instrum
ment artifacts (for more
information see ref. 19), I0(λ) is the refeerence spectrum, σi are cross-section spectra of known absorbers (including a
“Ring” spectrum), ci are the fitted concenntration parameters, P is a polynomial.
1.2 Maximizing overlap between photoon paths and absorber layers
The MAX-DOAS sensitivity is maximal for observations of trace gas layers at/near the instrumeent altitude, see Fig. 1.
The primary quantity of a MAX-DOAS m
measurement is the ‘slant column density’ (SCD), D = ∫ c( s) • ds , which
SCD
is the integrated concentration c along thhe light path s (or more realistically the average integratted concentration over
many possible light paths). In practice, the DOAS analysis takes into account a reference spectrum, which is ideally
collected in the zenith to minimize the am
mount of trace gas absorption that is removed from the measured
m spectrum. The
resulting ‘differential slant column denssity’ (dSCD) is the difference between the actual SCD D and the SCD of the
reference spectrum (see eq. 1.). Mobile MAX-DOAS allows to further increase signal-to-noise by moving the sensor
such that the spatial overlap between thee photon paths through an absorber layer is maximized. Airborne
A MAX-DOAS
systematically maximizes sensitivity towwards trace gas layers in the free troposphere, which can also
a be measured from
ship or from high-mountain observatoriess, though with reduced sensitivity compared to application ns from aircraft.
Mobile MAX-DOAS deployments pose tthe following experimental challenges: (1) for the quantiitative interpretation of
MAX-DOAS measurements accurate knnowledge of the elevation angle is needed. Past deploy yments of Ship MAX-
DOAS did either not quantify ship moveements,16,17 or suffered from a variable field of view duee to ship movements;18

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 either affects the quantitative interpretatioon of MAX-DOAS measurements from ships. (2) Record ding of the reference in
the zenith is not always possible. Past ddeployments of Airborne MAX-DOAS employed fixed telescopes;
t Fraunhofer
lines and stratospheric absorbers were eeliminated from the measured spectra by dividing by a “clean air” spectrum
recorded with some time delay in a differrent air mass. Such AMAX-DOAS instruments only measures variations relative
to an unknown tropospheric “clean air” SCD. Also, at elevated solar zenith angles (SZA), tim me delays between the
measured and reference spectrum can caause imprecisions in the correction of stratospheric absorber SCDs; as a result
tropospheric concentration gradients becoome entangled with stratospheric changes in path lengths distributions.
d

2. CU SHIP MA
AX-DOAS INSTRUMENT (CU SMAX-DOAS)
The components of CU’s Ship MAX-DO OAS are shown in Figure 2. It consists of a rotating prism m telescope (f/4), which
is mounted on the outside railing (Fig.2, bottom right), and coupled with a clinometer (bottom leeft) mounted inside the
ship, which provides pitch and roll anglees of the ship to the CompactRIO processor/computer. Th he two clinometers are
actively temperature controlled at 23 ± 0.25° C, resulting in negligible contributions of zero and sppan drifts to the overall
accuracy (zero drift < 0.002°; scale factorr drift <0.03%). The absolute sensor accuracy is 0.1° C.

Fig. 2. Spectral ranges covered by 3 sppectrometers (upper panel), and the inside and outside componen
nts of the CU Ship
MAX-DOAS (lower panel).

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 A custom built Labview RT code analyses these angles and adjusts the telescope position by turning the prism to account
for ship movements. The prism is mounted to the axis of a motor with microstepping capabilities (0.009° microstepping
width, and an inaccuracy of 0.05 * 360° / 200 = 0.09°), and the axis position is continuously monitored by means of an
internal encoder. The encoder precision is 1/2048 of a full revolution, or 0.17°, which is less than the actual motor
precision; if the encoder is not within 0.35° of the target position, an automatic reset is performed to assure the absolute
accuracy of the telescope motion compensation. The repetition rate of the real-time angle stabilization loop is 20Hz, and
limited by the speed of the clinometer measurement, which at present is about 3Hz. While this is sufficient for ship
movements, higher rates are needed to maintain good pointing accuracy from aircraft. The light is guided by optical
fibers into three OceanOptics QE65000 spectrometers, which are synchronized by a custom built Labview code. Three
spectral ranges that are simultaneously observed: ultraviolet (300-417nm), visible-blue (415-524nm), and visible-red
(526-634nm), each with an optical resolution of about 0.45nm FWHM. The trace-gases that can be simultaneously
measured by the instrument are shown in Fig.2, top panel.

The functionality of the motion compensation system was tested by means of a separate (third) clinometer that was
placed on top of the motion controlled telescope. The tests were performed at an elevation angle of zero degrees (line of
sight to the horizon) under conditions when waves acting on the ship caused the ship roll angle to vary by 6° (peak to
peak), and the pitch angle varied by 1.3° (peak to peak). The telescope was pointing near perpendicular to the ship
motion, and the roll angle variations very closely resemble the angle compensated by the motion compensation system.
The variability of the elevation angle could be determined with 0.1° precision, and was found to be 0.56° (1-sigma).

3. CU AIRBORNE MAX-DOAS INSTRUMENT (CU AMAX-DOAS)

The components of the CU Airborne MAX-DOAS instrument are shown in Figure 3. It consists of three telescopes that
are housed in a pylon (Fig.3, bottom right), and observe scattered solar photons in the zenith, nadir and forward viewing
direction via three prisms. The elevation angle of the forward looking prism can be adjusted to one of six positions,
which correspond to elevation angles between -6.5° and +6°; the angle is chosen before each flight to optimize the
observing strategy. Light from each telescope is coupled onto a 1.7mm core diameter optical quartz glass fiber; a forth
fiber provides light from a mercury lamp for calibration purposes. All four fibers are connected to a custom built optical
switch assemble (Fig.3 bottom middle panel), which consists of a high precision linear translation stage onto which a
single 1.7mm core diameter quartz optical fiber is mounted; the translation stage is coupled to a microstepper motor with
internal encoder. The linear movements of the stage allow the single fiber to be positioned precisely in front of one of
the four incoming fibers; the optical switch as such controls and allows to change the viewing angle/calibration lamp
observed by the instrument. The output fiber from the optical switch is coupled onto a bundle of 72 individual 145
micrometer core diameter quartz optical fibers, which are split into two bundles of 36 fibers. At these ends they are
vertically aligned and positioned in front of the entrance slits of two ACTON SP2150i spectrometers, and each
spectrometer is coupled to a TE cooled PIXIS400B CCD camera. Each spectrometer is equipped with a turret that holds
up to two grating, which can be turned to choose the wavelength range. The first spectrometer is equipped with a custom
made 1000grooves/mm grating, blazed at 250nm, and typically set to observe the wavelength range from 330 to 470nm
with an optical resolution of about 0.65nm FWHM; other spectral ranges are chosen depending on the specific
application. The second spectrometer is equipped with two custom made gratings: (1) 400 grooves/mm, blazed at
550nm, (2) 500 grooves/mm, blazed at 330nm. This spectrometer is typically set to observe the spectral range from
335nm to 640nm with an optical resolution of 1.5nm FWHM (grating 1). The first ACTON/PIXIS (A/P) system is used
to measure trace gases (Fig. 2, top panel); the second A/P system is used to measure the set of O4 and water bands. The
two A/P systems are both controlled from a custom built Labview code, and operated in a time synchronized mode. The
code actively controls the temperature of each spectrometer by means of separate PID loops, as well as the temperature
of the rack by means of three 70W peltier elements that are controlled in parallel as part of a single additional PID loop.
The spectrometers are typically heated to 37.5°C +- 0.1°C, to avoid condensation, and the rack temperature is cooled to
26°C +-0.2°C to compensate for variations in the temperature inside the fuselage during aircraft take-off and landing.
The Labview code controls, reads back and stores about 50 parameters; combining information from hardware
components (1) optical switch, (2) two ACTON spectrometers, (3) two PIXIS CCD cameras, (4) solid state relays of PID
loops, (5) temperature probes, (6) a GPS (timestamp), with (7) software control settings, (8) housekeeping data, and (9)
Solar Zenith Angle (SZA) into a single housekeeping file.

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 Fig. 3. The coomponents of the CU Airborne MAX-DOAS instrument.

4. RES
SULTS: SIGNAL TO NOISE TESTS
Solar straylight spectra from field and laaboratory experiments were analyzed using the WinDOA AS software.19 The
software performs a non-linear least squares fit by simultaneously adjusting the relevant atmospheric absorbers in
the respective wavelength range to the m measured spectra. To account for broad band effects (in paarticular caused by
Rayleigh- and Mie-scattering) a polynom mial of degree 3 was included. The fitting procedure is performed with the
logarithm of the spectra (i.e. in optical ddensity space). In some cases a pre-logarithmic linear inntensity offset was
included (see introduction). The fitted crooss sections include: two O3 cross section references (T = 223K and 243K),
two NO2 cross section references (T = 2220K and 294K), a water vapor and a glyoxal cross section, as well as a Ring
reference spectrum;20 a linear shift on thee measured spectrum was allowed during the fitting procedure. The 1-sigma
RMS noise of the residuals from these fitts is shown in Figure 4, left panel. The theoretical RMS noise
n is also shown
as a solid line. Field data were collectedd at a high mountain observatory in Colorado, and were evaluated using a
standard MAX-DOAS evaluation proceddure. The “laboratory data” represent solar straylight speectra recorded at a
constant elevation angle, and using diffferent saturation levels (constant over any single acqu uisition). Figure 4
demonstrates that for spectra collected at a constant elevation angle the RMS decreases as expected based on photon
counting statistics. At RMS values on thhe order of 1x10-4 near 350nm (5-8x10-5 near 450nm) th he RMS no longer
decreases as expected with increasing nnumber of photons, but instead it is found that it depend ds (approximately
linearly) on the difference in saturatioon levels between the two spectra. The saturation lev vel represents the
percentage number of the dynamic rangee of the 16-bit ADC at which the maximum of the spectrum was digitized
(in principle the wavelength range where the maximum is determined can be chosen in our Labview w code).

Fig. 4. Dependence of the RMS residuall noise of DOAS retrievals on the number of solar straylight ph hotons (left), and on
the difference (sample – reference) oof CCD saturation levels (see text) used to record the spectra (right).

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 Fig. 5. Correlation of residual structuress caused from incomplete elimination of Fraunhofer lines and the Ring spectrum.
Two solar straylight spectra are commpared accumulating an about equal number of photons (N = 10 1 10) by coadding of
CCD acquisitions at saturation levells of 50% (upper row), and using 10% or 90% saturation level (lower
( row). Two fit
scenarios were evaluated: (a) fit includes an “offset” and a “Ring” spectrum, (b) fit includes only th
he “Ring” spectrum.
Including an “offset” spectrum channges the scaling factor of the Ring spectrum, and the RMS remaains about five times
larger than the theoretical RMS noisse. Recordings at constant CCD saturation level results in the low
west RMS values.
In order to investigate RMS values smaaller 10-4 systematically, the number of photons N in sp pectra collected at
constant elevation angle were performedd at near constant N (within few percent). The right paanel shows results
where N = 1010 photons were collected uusing spectra taken at different saturation levels, and evaluuated near 350nm,
and 450nm using two fit scenarios: (blue) fit includes an “offset” and a “Ring” spectrum, (red) fitt includes only the
“Ring” spectrum. As is visible, the depenndence on the difference in saturation level is stronger near
n 350nm, where
the Fraunhofer lines are stronger; notablyy, this dependence is reduced, though not eliminated if an offset spectrum is
fitted in addition to the Ring spectrum.
Figure 5 demonstrates that the limitationn in RMS is caused by the fact that the apparent shape of Fraunhofer lines
depends on the saturation level at which sspectra are recorded. Spectra with N=1010 photons are com mpared. The upper
row of panels shows results from two sppectra that were recorded at identical saturation level of o 50%. The RMS
noise is within few 10% of the theoreticcal noise, and including an offset in the fit has virtually y no effect on the
attainable RMS noise level. The lower row w shows results from two spectra that were recorded at a saturation level of
10% and 90%. Here, the RMS noise is five times higher than the theoretical noise, and including an offset in the fit
has a pronounced effect to (artificially) loower the RMS noise level by about a factor of two. Moreover, the spectral
shape of the fitted offset spectrum is sttrongly anti-correlated with the Ring spectrum, and inccluding the offset
spectrum has a strong effect on the valuue of the Ring fit coefficient. Regardless of the fact thatt a small Ring fit-
coefficient is expected (i.e., spectra recorrded within few 10 mins at constant elevation angle, and mostly clear sky),
the ring fit coefficient is more than 10 ttimes greater, and of opposite sign if the spectra are reccorded at different
saturation levels. This increase in RMS ccannot be explained by atmospheric absorbers, which aree accounted for in
the analysis procedure, and is a strong i ndication that nonlinearities in the detector limit the waay that Fraunhofer
lines can be characterized with available sstate-of-the-art CCD detectors.

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 5. RESULTS: RADIATIVE TRANSFER CALCULATIONS
A method to estimate concentration units near instrument altitude without the need to involve inverse methods would
provide computationally efficient means to define a starting point for refined analysis using inverse methods, and
significantly advance the use of MAX-DOAS by providing a unit that is typically used to characterize the chemical
status of the atmosphere, and predicted by atmospheric models. The following approach leverages the fact that under
certain conditions measurements of trace gases with a known distribution in the atmosphere can provide direct means to
convert column amounts measured near instrument altitude (units of molec cm-2) into units of concentrations or parts per
trillion (10-12 volume mixing ratio; 1 ppt = 2.46x107 molec cm-3 at a pressure of 1013 mbar, and a temperature of 298 K).
Radiative transfer calculations were performed for the following parameters retrieving differential air mass factors for O4
(as an indicator for the aerosol load11-13) and a weak absorbing trace gas at the same wavelengths (360 and 477 nm): box
profiles (i.e. constant value up to a certain height and zero above) were assumed for both the aerosol and the weak
absorbing trace gas with heights of 500m, 1000m and 2000m. The surface albedo was 5%, the single scattering albedo
97% and the asymmetry parameter 0.75, which is typical value for marine aerosols.21 The sun was assumed to shine
constantly perpendicular to the measurement direction plane meaning a relative azimuth angle of 90°. The full opening
angle of the imaginary telescope was 0.4°. The concentration of the trace gas was retrieved by calculating the path length
s through the trace gas layer by means of differential O4 air mass factors dAMFO4 and O4 concentrations cO4: s =
dAMFO4 x VCDO4 / cO4. According to the US standard atmosphere the vertical column density VCDO4 was 1.33 ⋅ 1043
molec2/cm5. cO4 was approximated to an average concentration of 2.7 ⋅ 1037 molec/cm3 for 500m layer height, 2.6 ⋅ 1037
molec/cm3 for 1000m and 2.4 ⋅ 1037 molec/cm3 for 2000m. The concentration of the trace gas cTg was retrieved by using
s as follows: cretrieved = dAMFgas x VCDgas / s, with dAMFgas and VCDgas as differential air mass factors and vertical
column density of the trace gas, respectively. In Figure 6 this value was divided by the concentration c of the trace gas
which was given as input into the calculation. Figure 6 demonstrates that the ratio f = cretrieved / c is below unity in
virtually all cases studied. More importantly f becomes independent of the elevation angle with increasing aerosol
optical depth. At 20° SZA the ratio converges onto a relatively constant number (varies by <10% for angles ≤ 3.8)
already at an aerosol optical depth of 0.3 (typical for the marine boundary layer); i.e., at 360nm this corresponds to
values of 0.4 for 500m, 0.6 for 1000m, and 0.74 for 2000m; at 477nm this corresponds to values of 0.5 for 500m, 0.68
for 1000m, and 0.78 for 2000m.

The factor f can be rationalized as a correction factor to derive accurate concentrations as ccorr = cretrieved / f; it is a
convoluted quantity that accounts for differences in the vertical profile of O4 and the trace gas among other factors.
Notably, at 360nm f360nm = 0.57 is suited to derive the trace gas concentration within 25%; at 477nm the dependence on
boundary layer height is even smaller, and f477nm = 0.64 gives results within better 20% over the range of boundary layer
heights studied. We conclude that a value of f = 0.6 is representative for overhead sun conditions, and gives results
within 30% that are independent of wavelength and boundary layer height. Sensitivity tests that varied SZA showed that
f converges between different elevation angles also at higher SZA, with values of f approaching unity at higher aerosol
optical depth.

6. CONCLUSIONS
Two approaches are investigated to maximize the signal-to-noise of using MAX-DOAS to measure trace gas layers of
weak absorbers: (1) Airborne MAX-DOAS allows to maximize the spatial overlap between the photon paths through
absorber layers. (2) A novel software tool was developed to actively lower the attainable noise level from DOAS
retrievals using solar straylight photons; the software overcomes existing limitations towards lowering the noise level by
actively controlling the saturation level of measured spectra within narrow bounds. It is demonstrated that this is needed
to characterize Fraunhofer lines in a consistent way, and RMS values as low as 2x10-5 are demonstrated for
measurements at constant elevation angle. Active controls of the saturation level are a prerequisite to use the information
contained in the Ring effect to infer aerosol optical properties. The University of Colorado Ship MAX-DOAS and
Airborne MAX-DOAS instruments provide two innovative, and flexible mobile MAX-DOAS instruments that are well
suited to measure the column abundance of reactive gases like CHOCHO, IO, BrO and other gases that are of relevance
to atmospheric composition in urban, remote and marine air, as well as their vertical distribution throughout the free
troposphere.

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 Fig. 6. Retrieving trace-gas concentrations are compared to a-priori concentrations for box-vertical profiles of different
height, and as a function of the wavelength where the gas is retrieved: 360nm (left column); 477nm (right column);
boundary layer height of 0.5km (panels a,d), 1km (b,e), and 2km (c,f).

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