Geophysical Research Letters
RESEARCH LETTER
10.1029/2018GL077823
Key Points:
• Airglow from the oxygen band
at 1.27 micron is accurately
reconstructed and validated using
SCIAMACHY
• Airglow has to be included in the
nadir retrieval and can be adequately
separated from absorption by oxygen
column
• Spaceborne greenhouse gas sensing
should reconsider including the
1.27 micron band for better light path
constraint
Supporting Information:
• Supporting Information S1
Correspondence to:
K. Sun,
kangsun@buffalo.edu
Citation:
Sun, K., Gordon, I. E., Sioris, C. E., Liu,
X., Chance, K., & Wofsy, S. C. (2018).
Reevaluating the use of O2 a1 Δg
band in spaceborne remote sens-
ing of greenhouse gases. Geophysical
Research Letters, 45, 5779–5787.
https://doi.org/10.1029/2018GL077823
Received 8 MAR 2018
Accepted 17 MAY 2018
Accepted article online 24 MAY 2018
Published online 13 JUN 2018
©2018. American Geophysical Union.
All Rights Reserved.
SUN ET AL.
Reevaluating the Use of O2 a1 Δg Band in Spaceborne Remote
Sensing of Greenhouse Gases
Kang Sun1,2 , Iouli E. Gordon2 , Christopher E. Sioris3 , Xiong Liu2 , Kelly Chance2 ,
4
and Steven C. Wofsy
1 Research and Education in eNergy, Environment and Water Institute, University at Buffalo, Buffalo, NY, USA,
2 Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA, 3 Environment and Climate Change Canada, Toronto,
Ontario, Canada, 4 School of Engineering and Applied Sciences and Department of Earth and Planetary Sciences, Harvard
University, Cambridge, MA, USA
Abstract Although the O2 a1 Δg band has long been used in ground-based greenhouse gas remote
sensing to constrain the light path, it is challenging for nadir spaceborne sensors due to strong mesosphere/
stratosphere airglow. Spectroscopic simulations using upper state populations successfully reconstruct
the airglow spectra with excellent agreement with SCanning Imaging Absorption spectroMeter for
Atmospheric CHartographY limb observations (residual root-mean-square <0.7%). The accurate knowledge
of airglow spectrum enables retrieval of O2 (a1 Δg ) number density, volume emission rate, and temperature.
For nadir spaceborne observations, the a1 Δg airglow will lead to a negative bias of ∼10% to O2 column,
if not considered. However, when properly included, the airglow spectral feature can be adequately
separated from O2 absorption (mean bias <0.1%) at the spectral resolution of modern spaceborne
spectrometers.
Plain Language Summary Carbon dioxide (CO2 ) and methane are two of the most important
anthropogenic greenhouse gases. Highly accurate global-scale spaceborne measurements using
backscattered sunlight are needed to adequately quantify the sources and sinks of CO2 and methane,
which are still poorly understood. To achieve the required accuracy, atmospheric oxygen needs to
be measured simultaneously to constrain the path length of the backscattered sunlight through the
atmosphere. The best oxygen band for this purpose, the a1 Δg , or singlet Delta, band at 1.27 μm, has long
been deemed unusable in spaceborne measurements, due to the intense and uncertain airglow emitted
from the upper atmosphere at the same wavelength. This study characterizes the spectral shape and spatial
distribution of airglow using recent satellite observations and concludes that the contamination of airglow
can be adequately separated from the backscattered sunlight without significant loss of precision and
accuracy. The use of the singlet Delta band will substantially simplify the design of spaceborne greenhouse
gas instruments, reduce the cost, and potentially make more accurate greenhouse gas retrievals. As such,
we call on the greenhouse gas remote sensing community to reconsider the oxygen singlet Delta band
in future missions.
1. Introduction
Carbon dioxide (CO2 ) and methane (CH4 ) are two of the most important anthropogenic greenhouse gases.
However, the spatiotemporal variations in their sources and sinks are poorly understood, leading to signif-
icant uncertainties in projections of future climate trends (Eldering et al., 2017; Miller et al., 2007; Turner
et al., 2017). Spaceborne remote sensing using backscattered sunlight enables global-scale observations of
CO2 and CH4 with sensitivity to the lower troposphere and hence provides unprecedented constraints on
the global carbon cycle (Jacob et al., 2016; Miller et al., 2007). To separate the sources/sinks of CO2 and
CH4 from variations of surface pressure and specific humidity, the abundances of CO2 and CH4 are usually
represented by the column-averaged dry mole fractions (XCO2 and XCH4 ). To sufficiently constrain their distri-
butions and trends through inverse modeling, XCO2 has to be retrieved to a precision of 0.25–0.5% (1–2 ppmv;
Crisp, 2008; Frankenberg et al., 2015; Miller et al., 2007), and XCH4 has to be retrieved to a precision of
better than 1% (20 ppbv; Bergamaschi et al., 2007, 2009; Hu et al., 2016) without significant geographically
varying biases.
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Scattering by optically thin clouds and aerosols poses a substantial challenge to the accurate retrievals of XCO2
and XCH4 by altering the light path. Various physics-based retrieval approaches that account for atmospheric
scattering have been applied to existing observations, including those from SCanning Imaging Absorption
spectroMeter for Atmospheric CHartographY (SCIAMACHY; Reuter et al., 2010), Greenhouse Gas Observing
Satellite (GOSAT; Butz et al., 2011; Heymann et al., 2015; Yoshida et al., 2011), Orbiting Carbon Observatory-2
(OCO-2; Boesch et al., 2011; Connor et al., 2008; Jung et al., 2016; Kuang et al., 2002; O’Dell et al., 2012), and
TROPOspheric Monitoring Instrument (TROPOMI; Hu et al., 2016) and proposed as part of future missions
such as Carbon Monitoring Satellite (CarbonSat; Buchwitz et al., 2013), Geostationary Carbon Observatory
(GeoCarb; Polonsky et al., 2014), Geostationary Fourier Transform Spectrometer (GeoFTS; Xi et al., 2015), and
Geostationary Emission Explorer for Europe (G3E; Butz et al., 2015). All of these studies use simultaneous mea-
surements of the O2 A band at 0.76 μm, as O2 is an excellent light path proxy due to its constant mixing ratio
throughout the atmosphere. For CH4 detection at the 1.65 μm band, it is also possible to use CO2 as light path
proxy at 1.6 μm, but this “proxy” approach relies on a strong assumption that XCO2 can be accurately estimated
through models (Frankenberg et al., 2006; Jacob et al., 2016; Parker et al., 2015).
While the O2 A band has been traditionally used in satellite remote sensing, the O2 a1 Δg band near 1.27 μm
may be a more optimal choice, due to its proximity to the CO2 /CH4 bands at 1.6–1.7 μm and the stronger
CO2 /CH4 bands between 2.0 and 2.4 μm. Reducing the spectral spacing between the O2 and CO2 /CH4 bands
will inherently minimize the differences in aerosol and cloud optical properties between the two. In addition,
the reduced spectral spacing may also enable simpler instrument design and potentially reduce the cost of the
payload. Compared to the CO2 /CH4 bands, the O2 A band is much stronger and largely saturated, causing chal-
lenges in the spectroscopic fitting (Drouin et al., 2017). The O2 a1 Δg band, however, is generally much weaker
with a still saturated Q branch to provide a wide range of sensitivity to scatterers at different altitudes. The
O2 a1 Δg band has been used by ground-based, direct-solar-viewing Total Carbon Column Observing Network
(TCCON) sites all over the globe for over a decade (Wunch et al., 2011) and by the nadir-viewing California
Laboratory for Atmospheric Remote Sensing Fourier transform spectrometer (CLARS-FTS) system at Mount
Wilson, California, since May 2010 (Fu et al., 2014).
However, the O2 a1 Δg band has long been deemed unusable for spaceborne greenhouse gas measurements
due to the intense airglow emitted in the upper atmosphere (Kuang et al., 2002; Wunch et al., 2011). Uncertain-
ties in spectral and spatial (both vertical and horizontal) characteristics of airglow hampered its consideration
when the first generation of greenhouse gas satellites were proposed (Kuang et al., 2002; Noxon, 1982).
In addition, change in airglow intensity at very small spatiotemporal scales due to gravity waves (Hines &
Tarasick, 1987; Thomas et al., 1984) may present substantial challenges to the retrieval process. Over the recent
years, much more comprehensive spaceborne observations of airglow have been performed by the Optical
Spectrograph and Infrared Imager System (OSIRIS) instrument aboard the Odin satellite (Llewellyn et al., 2004)
and the SCIAMACHY instrument aboard the Envisat (Bovensmann et al., 1999). Wiensz (2005) derived ver-
tical distribution of O2 (a1 Δg ) concentrations at global scale using OSIRIS limb observations and found that
O2 (a1 Δg ) peaks near the stratopause where the impact of gravity waves is weak. However, OSIRIS only has two
channels in the O2 a1 Δg band and therefore provides little constraint on the spectral shape of airglow. Zarboo
et al. (2018) retrieved mesosphere/thermosphere (50–150 km) airglow emission spectra using SCIAMACHY
limb observations assuming no self-absorption, whereas O2 (a1 Δg ) airglow is also present in the stratosphere
with significant self-absorption. As such, we propose a physics-based method to model high-resolution air-
glow emission spectrum using available spectroscopic parameters from the HIgh-resolution TRANsmission
molecular absorption database 2016 (HITRAN2016; Gordon et al., 2017). Using the airglow simulation as a for-
ward model, temperature and O2 (a1 Δg ) concentrations are retrieved from SCIAMACHY limb data to assess the
spatial variation of airglow and impact of gravity waves. Finally, airglow is included in nadir radiance simulation
to quantify the impact of airglow on O2 column retrieval in spaceborne nadir observations.

2. Data and Methods

2.1. SCIAMACHY Limb Observation
The SCIAMACHY is an eight-channel grating spectrometer that measures scattered sunlight in limb and
nadir geometries from 240 to 2,380 nm. In this study, only limb measurements covering the O2 a1 Δg band
(1,230–1,320 nm) in the spectral channel 6 (1,050–1,700 nm) are used. The instrument line shape (ILS) of this
channel is Gaussian with a full width at half maximum (FWHM) of about 1.5 nm (Bovensmann et al., 1999;
Rozanov et al., 2011).

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In normal limb viewing geometry, SCIAMACHY tangentially observes the atmosphere from the surface up
to about 100 km with a vertical step of 3.3 km. At each tangent point, the vertical resolution is 2.6 km,
the horizontal along-track resolution is about 400 km, and the horizontal cross-track resolution is 240 km. To
improve the signal-to-noise ratio, the four cross-track spectra at the same elevation step are coadded, reduc-
ing cross-track resolution to 960 km (i.e., the swath width). Limb radiances are spectrally and radiometrically
calibrated using EnviView 2.2.7 (Sioris et al., 2006).

2.2. Modeling Airglow Spectra

The radiance spectrum from SCIAMACHY limb observation (Rg , in photons/cm2 /nm/sr/s) at tangent height
H is an integration of local monochromatic airglow volume emission rate spectra (rg , in photons/cm3 /nm/s)
along the line of sight:

1 ∑
∞
Rg (H, 𝜆) = r (h, 𝜆) (h)L(h), (1)
4𝜋 h=H g

where the altitude grid (h, in cm) is usually defined by the SCIAMACHY tangent height levels for convenience,
 (h) is the transmission from the layer above h to the top of atmosphere along the line of sight, L(h) is the path
length of the line of sight through the layer at h, and 𝜆 is wavelength in nanometers. The airglow is assumed to
be isotropic. The volume emission rate (VER, in photons/cm3 /s) is the integration of rg over the entire band, and
the O2 (a1 Δg ) number density is just the VER divided by the electronic-vibrational Einstein A coefficient (2.27×
10−4 s−1 , calculated from HITRAN2016 individual line intensities using equations 18 and 32 from Gamache &
Goldman, 2001). The O2 a1 Δg state has a long lifetime (73 min), which assures that the molecule is in rotational
equilibrium with the ambient atmosphere (Kaufmann et al., 2018). A simplified assumption is that rg scales
with the absorption cross section:
∑
rg (𝜈) = C0 Sij (T)f (𝜈, 𝜈ij , T, p), (2)
ij

where Sij (T) is the line intensity for transition ij and f (𝜈, 𝜈ij , T, p) is the normalized line shape function. The
Voigt profile is used in this study. C0 is a scaling factor to match the absorption cross section to the observed
rg . Here the dependency of rg on altitude (h) is dropped as both temperature (T ) and pressure (p) are defined
at the altitude grid. A wave number coordinate (𝜈 in cm−1 ) is used to be consistent with HITRAN. Very high
resolution grid (0.001 cm−1 or 0.0002 nm) is needed to resolve the narrow lines broadened mainly by Doppler
effect at airglow altitudes.
The line intensity given by HITRAN is derived assuming local thermal equilibrium (Hill et al., 2016; Šimečková
et al., 2006):
Aij g′ exp(−c2 Ei ∕T)(1 − exp(−c2 𝜈ij ∕T))
Sij (T) = Ia , (3)
8𝜋c𝜈ij2 Q(T)

where the natural isotopic abundance, Ia , speed of light, c, and total internal partition sum, Q(T), are constants
and will be normalized out. The transition wave number 𝜈ij varies very little over the band, and hence, the term
1∕𝜈ij2 has insignificant contribution to the spectral variation. Aij is the Einstein A coefficient, which, unlike inten-
sity Sij , is independent of whether local thermal equilibrium is assumed or not. The term g′ exp(−c2 Ei ∕T)∕Q(T)
is the relative population of molecules at lower state energy Ei , where c2 = 1.4387770 cm K and g′ is upper
state statistical weight. At Earth’s atmospheric temperature, the induced emission term, 1 − exp(−c2 𝜈ij ∕T), is
effectively unity for electronic transitions and can be neglected (Gamache & Goldman, 2001).
Although O2 molecules at the a1 Δg state (i.e., upper state) are in rotational equilibrium, the rovibronic states
are not populated thermally as assumed in the line intensity definition (equation (3)). At atmospheric temper-
atures, the thermal population of the upper state is negligibly small (∼10−20 of the ground-state population).
Instead, the upper state population is generated from photolysis of ozone at wavelength <310 nm (Ball
& Hancock, 1995), reaching ∼10−5 of the ground-state population. Therefore, the airglow emission should
be defined by the relative population at the upper state (Nj ), instead of the lower state as incorporated in
equation (3), and the Einstein A coefficient:
∑
rg (𝜈) = Nj Aij f (𝜈, 𝜈ij , T, p). (4)
ij

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Here we assume that the chemically generated O2 (a1 Δg ) molecules all start at the first allowed
energy level of the excited state, which coincides with the band origin of the a1 Δg -X 3 Σ−g (0,0) band
(𝜈0,0 = 7883.756645(113) cm−1 (Leshchishina et al., 2010)). Note that the (1,1) band is also included in our
analyses. Assuming that the thermal population into the upper state energy levels (Ei + 𝜈ij ) follows Boltzmann
distribution:
g′ exp(−c2 (Ei + 𝜈ij − 𝜈0,0 )∕T)
Nj = n(O2 (a1 Δg )) . (5)
Q(T; airglow)

Here n(O2 (a1 Δg )) is the O2 (a1 Δg ) number density. Q(T ; airglow) is a partition sum within the a1 Δg state
(setting the band origin to zero) and calculated using data from Yu et al. (2014).
When O2 self-absorption is neglected, rg from all layers are linearly inverted from SCIAMACHY observations
(Rg ) at all the tangent heights (supporting information Text S1). Then n(O2 (a1 Δg )) and temperature are directly
retrieved from rg using equations (4) and (5) as forward model. Otherwise, equations (1), (4), and (5) have
to be combined as the forward model to directly match Rg at progressively lower tangent height (i.e., the
“onion-peeling” approach, see Text S1) and rg is not explicitly calculated. A Levenberg-Marquardt nonlinear
least squares algorithm (Sun et al., 2017) is applied in both cases to retrieve n(O2 (a1 Δg )), temperature, ILS
width, and a spectral shift.

3. Results
3.1. Deriving Airglow Variations From SCIAMACHY
Figure 1 shows the fitting of rg in the upper (83.8 km, a and b) and lower (60.9 km, c and d) mesosphere,
where rg is derived using linear inversion. This approach assumes no self-absorption to airglow and is accurate
above ∼60 km. There is a clear mismatch (>5%) between rg simulated using equations (2) and (3) (blue curves)
and inverted SCIAMACHY rg (black dots). The population observed in the P branch is larger than the simu-
lation, whereas the population observed in the R branch appears to be smaller. When using the upper state
population, as in equations (4) and (5), the simulation (red curves) closely agrees with SCIAMACHY with resid-
ual root-mean-square (RMS) <0.7%. The impact of temperature (labeled in Figures 1a and 1c) on the airglow
spectral shape is also visible.
The airglow retrievals are repeated for SCIAMACHY orbit #44801 on 24 September 2010. Figure 2a shows the
vertical-meridional distribution of O2 (a1 Δg ) number density derived from the onion-peeling approach. The
spatial distribution and absolute values of O2 (a1 Δg ) are consistent with the OSIRIS observations and model
simulations from Wiensz (2005). Figure 2b compares the VER derived by onion peeling (black curve) and from
linear inversion (red curve, from integration of the linearly inverted rg ) at scan #12 located at 46∘ N, 169∘ W.
The linear inversion gives very similar results in the mesosphere but inaccurate (and some negative) val-
ues in the stratosphere. The agreement between the two approaches validates our implementation of the
onion-peeling algorithm, and the mismatch at stratosphere/lower mesosphere confirms that self-absorption
should be considered to study the complete vertical profile of O2 (a1 Δg ) airglow. Shown in light gray in
Figure 2b are VER profiles derived by onion peeling from scans #11–18, which cover a latitude range of
60∘ –2∘ N, and a solar zenith angle range of 62∘ –29∘ . These VER profile shapes are very similar. The weak depen-
dencies of VER and O2 (a1 Δg ) number density on the solar zenith angle are consistent with previous studies
(Wiensz, 2005; Zarboo et al., 2018), because the ozone photolysis is optically thin at the airglow altitudes. The
insignificant variations of VER and O2 (a1 Δg ) also indicate that the gravity waves do not have a strong impact
on the overall intensity of O2 (a1 Δg ) airglow.
However, gravity waves modulate the atmospheric temperature, bringing about uncertainties in the spec-
tral shape of airglow even when VER and O2 (a1 Δg ) number density are invariant. As shown in Figure 1, the
spectral shape of rg can be accurately modeled using equations (4) and (5). This enables retrieval of tem-
perature from airglow spectra with uncertainties <5 K. Figure 2c compares the mesospheric temperature
(above 60 km) retrieved using onion peeling (color-coded dots) with collocated temperature profiles from
the Mass Spectrometer Incoherent Scatter (MSIS) model (Hedin, 1991; color-coded lines). To isolate the vari-
ation due to gravity waves from large-scale features, temperatures from a group of scans (#15–21) over the
tropics (24∘ N–20∘ S) with similar solar zenith angles (29∘ –38∘ ) are displayed together. The derived temper-
ature shows larger variations at higher altitudes due to gravity waves, which is not captured by the MSIS
model. Nevertheless, the mean of the ensemble of derived temperature agrees well with the MSIS model.

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 Geophysical Research Letters 10.1029/2018GL077823

10 4
(a) 83.8 km, 198.6 K 10 6
(c) 60.9 km, 242.1 K

12 SCIAMACHY SCIAMACHY
2

r g [photons cm -3 s-1 nm-1 ]

r g [photons cm -3 s-1 nm-1 ]

Equations 2-3 Equations 2-3
10 Equations 4-5 Equations 4-5
1.5
8

6 1

4
0.5
2

0 0
Relative to peak radiance

Relative to peak radiance

(b) Relative residual (d) Relative residual
0.05 0.05
0 0
-0.05 -0.05

1240 1250 1260 1270 1280 1290 1240 1250 1260 1270 1280 1290
Wavelength [nm] Wavelength [nm]

Figure 1. (a) Fitting of rg at 83.8 km (SCIAMACHY orbit #44801, scan #18) using equations (2) and (3) (blue), and (4)
and (5) (red). (b) Relative residuals of fits. (c and d) The same as (a) and (b) but for 60.9 km. The RMS of fitting residual
using equations (4)–(5) is 0.7% of the peak airglow radiance at 83.8 km (the red line in (b)), dominated by observational
error, and 0.4% of the peak airglow radiance at 60.9 km (the red line in (d)), dominated by systematic error.
SCIAMACHY = SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY; RMS = root-mean-square.

The standard derivation of temperatures from these seven scans at each layer are calculated, smoothed by
lowess method with a length scale of 10 km, and multiplied by a factor of two to account for unsolved
subpixel-scale gravity wave features. This temperature uncertainty term is shown as gray dashed lines in
Figure 2c and saved for the following analysis to account for gravity wave perturbations in the airglow spec-
trum simulation. A uniform uncertainty of 5 K is used below 60 km, where the retrieved temperature is
increasingly uncertain, but the prior knowledge of atmospheric temperature is rather accurate.

3.2. Simulation Test of Airglow Impact on Nadir O2 Column Retrieval

After the derivation of VER profile and the spectral shape of rg , the top-of-atmosphere airglow radiance
observed at nadir can be calculated using equation (1). Figure 3 compares the airglow radiance (red) with
the backscattered solar radiance with an solar zenith angle of 45∘ and surface albedo of 45% (blue) for
nadir-viewing geometry. Details in the simulation of airglow/backscattered radiances are given in Text S2.

(a) (b) (c)

90 90 90
VER by onion-peeling
80 10
10 Variation of VER 0-60° N 80 80
VER by linear inversion
density [molec/cm ]
3

5
Altitude [km]

70 70 70
Altitude [km]

Altitude [km]

60 3 60 60

2 24 2 -20
g

50 50 50
Latitude
1

1
O2 a

MSIS model T
40 0 40 Retrieved T 40
T variability
30 30 30
-80 -40 0 40 80 0 5 10 160 180 200 220 240 260 280
6
Latitude VER [photons cm -3 s -1 ] 10 Temperature [K]

Figure 2. (a) O2 (a1 Δg ) number density retrieved from SCIAMACHY orbit #44801 by onion peeling. (b) Vertical profiles of VER retrieved using linear inversion (red)
and onion peeling (black) for scan #12. VER profiles from scans #11–18 are shown as light gray curves. (c) Mesospheric temperature (above 60 km) retrieved
using onion peeling (color-coded dots) and collocated temperature profiles from the MSIS model at 1:30 UTC (color-coded lines). Results from seven scans over
the tropics (#15–21) are shown. The dash gray lines indicate an estimation of temperature perturbation by gravity waves; see text for details.
SCIAMACHY = SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY; VER = volume emission rate.

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 Geophysical Research Letters 10.1029/2018GL077823

(a) Simulation of a1 radiance 10 13

10 13 g (b) Zoom-in at individual lines
Radiance [photons cm -2 s-1 sr-1 nm-1 ]

Radiance [photons cm -2 s-1 sr-1 nm-1 ]

3 3
Reflected radiance, = 0.45, SZA = 45
Airglow radiance, VZA = 0
2.5 2.5

2 2

1.5 1.5

1 1

0.5 0.5

0 0
1250 1260 1270 1280 1290 1268.75 1268.8 1268.85 1268.9
Wavelength [nm] Wavelength [nm]

Figure 3. (a) Airglow radiance (red) and backscattered solar radiance (blue) at nadir. Spectra are shown at native resolution (no instrument line shape applied).
(b) Similar to (a) but shows details at individual transitions. SZA = solar zenith angle; VZA = viewing zenith angle.

At infinitesimal resolution, the absorption is significantly saturated at the strongest transitions, and the
absorption lines are much broader than the airglow emission lines due to collisional broadening at the
lower atmosphere (Figure 3b). Therefore, the airglow can be readily separated from the absorption features.
For lower spectral resolution, the spectral shape of airglow becomes increasingly similar to the absorption
of O2 . To test the impact of airglow for different sensor configurations, we spectrally degrade the “true”
radiance using Gaussian ILS with different FWHM, interpolate the convolved spectra to spectral sampling
intervals at FWHM/3, and introduce random observational noise generated using different levels of effective
signal-to-noise ratio (SNRe , defined at 2 × 1013 photons/cm2 /nm/sr/s and reference spectral sampling inter-
val of 0.05 nm; see Text S2). For each combination of SNRe (200–2,000) and spectral sampling (0.01–0.1 nm),
an ensemble of 500 realizations of observed radiance are simulated. For each realization, four nonlinear least
squares retrieval cases are performed to minimize the error-weighed square of residuals (see Text S3 for
detailed algorithm description):
1. Assuming the airglow emission spectra are perfectly known. The slant columns of O2 , water vapor, a scaling
factor to the airglow spectrum, and the albedo mean/slope terms are retrieved.
2. Same as case 1 but an airglow spectrum calculated from absorption cross section (equations (2) and (3))
instead of equations (4) and (5) is used in the retrieval. See Figure 1 for their spectral difference.
3. Same as case 1 but when generating the ensemble of observations, the temperature profile of airglow is per-
turbed with the 1𝜎 uncertainty term shown in Figure 2c and an error correlation length scale of 7.5 km, that
is, the scale height. Compared to case 1, this case reveals the upper limit of the impact from mesospheric
gravity waves.
4. Airglow is neglected in the retrieval.
Note in these cases, the O2 columns are retrieved from O2 lines only. An independent scaling factor to the O2
collision-induced absorption (CIA) spectrum is also fitted, similar to ground-based O2 column retrieval (Yang
et al., 2002). It is possible to use CIA to provide additional constraint to O2 column, which we will defer to
future studies.
Figure 4 shows the RMS (fist row) and mean value (second row) of the relative O2 column biases ((retrieved
O2 column − true O2 column)/true O2 column) from the ensemble retrievals for different SNRe and spectral
sampling. The four columns in Figure 4 correspond to the four retrieval cases discussed above.
The RMS of relative biases show the combined effects of retrieval precision and accuracy. For cases 1 and 3,
the RMS is dominated by random errors, as the mean of biases is within ±0.1% and shows little dependency
on SNRe and spectral sampling (Figures 4e and 4g). This reassures that once included in the retrieval, the air-
glow can be adequately separated from the O2 absorption feature without introducing significant biases. This
can be explained by the fact that the airglow emission feature, even at reduced spectral resolution, is nar-
rower than the O2 column absorption feature. Other variables (CIA, surface reflectance, aerosol, and clouds)
produce much broader features and cannot explain the spectrally sharp residuals from airglow (Figures S2
and S3). The RMS of case 3 is similar to case 1 at lower SNRe but gets significantly higher at larger SNRe

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 Geophysical Research Letters 10.1029/2018GL077823

(a) RMS, (b) RMS, (c) RMS, (d) RMS,

Perfectly known airglow Absorption cross section Gravity wave Neglecting airglow
2000
1 1 1

0.2

9.2
10

0.2

Relative RMS [%]

0.8 0.8 0.8
1500 9.8
0.6 0.6 0.6

0.1
SNRe

9.6
0.4 0.4 0.4
1

0.1

9.2
1000
0.

9.4
0.2 0.2 0.2

9.4
9.6
9.8

10
9.2
0.2 2
500 3
0.0. 0.
2 .3
00 0. 0.3
4 .4 0.4
0.6 0.8 0.6 0.8 0.6 0.8

(e) Mean Bias, (f) Mean Bias, (g) Mean Bias, (h) Mean Bias,
Perfectly known airglow Absorption cross section Gravity wave Neglecting airglow
2000
0.05

-9.2

0.05
0

-10.1
-9.9
-9.3

-9.7
-9.5
0

0.05

Relative bias [%]

1500 0.1 0.1 0.1 -9.4
SNRe

-9.6
0

-0.05
1000 0 0 0 0
-9.8

-9.3
0

-0.05
0

0.0
5
0.05

0
-0.1 -0.1 -0.1
-0 -0.0 -10

5
500 .05

5
0 05

0.0
0. 0

0.02 0.04 0.06 0.08 0.1 0.02 0.04 0.06 0.08 0.1 0.02 0.04 0.06 0.08 0.1 0.02 0.04 0.06 0.08 0.1
Spectral sampling, , [nm] Spectral sampling, , [nm] Spectral sampling, , [nm] Spectral sampling, , [nm]

Figure 4. (a–d) RMS of the relative O2 column biases retrieved for cases 1–4. (e–h) Mean of relative O2 column biases retrieved for cases 1–4. Note the color
scales of case 4 are different from the other cases. The SNRe is defined at 2×1013 photons/cm2 /nm/sr/s and reference spectral sampling interval of 0.05 nm.
RMS = root-mean-square; SNR = signal-to-noise ratio.

(Figures 4a, 4c, and Figure S4), indicating that mesospheric temperature perturbed by gravity waves may
introduce extra errors if not accounted for. The gravity wave perturbation simulated in this case can be con-
sidered as an upper boundary (Figure S1a). The RMS of case 2 (Figure 4b) is also larger than case 1 (by >50%
at lower resolution, see Figure S4), and the mean bias from case 2 shows some systematic pattern (Figure 4f ),
demonstrating the benefits of accurately reconstructing airglow spectral shape using equations (4) and (5).
The RMS of case 4 is dominated by the retrieval bias, reaching −10%, because the airglow emission lines fill in
the O2 absorption lines, acting like a negative absorber. Evidently, airglow has to be properly represented in
the retrieval to mitigate its interference. Even at the same SNRe , finer spectral resolution improves O2 column
precision, indicated in Figures 4a–4c, by better separating airglow and O2 absorption.
One should also note that this simple retrieval test does not include any a priori influence. We expect that
the fitting precision will be improved using an optimal estimation-based retrieval, as the spectra and spatial
distribution of airglow can be well characterized a priori (Figure 2). Global airglow climatology can be readily
derived by extending the airglow retrieval demonstrated in this study to other SCIAMACHY limb orbits and
from OSIRIS (Wiensz, 2005). The knowledge on airglow will be further improved by future high spectral res-
olution nadir observations over the ocean, where the backscattered sunlight is much weaker than over land
due to low ocean albedo. Due to its coarse spectral resolution (∼1.5 nm), we are unable to separate airglow
and O2 absorption using SCIAMACHY nadir observations, but we expect future spaceborne sensors to have
sufficient resolution over the O2 (a1 Δg ) band.

4. Conclusions and Discussion

The O2 (a1 Δg ) airglow spectrum is accurately reconstructed from parameters available in the HITRAN
database. This airglow spectrum model shows excellent agreement with SCIAMACHY limb observations,
enabling the retrieval of O2 (a1 Δg ) number density, VER, and temperature, which can be used to study gravity
wave dynamics. Nadir observations are simulated combining both backscattered sunlight and airglow over
a range of instrument configurations. Retrieval tests using synthetic observations show that the mean bias is
<0.1% when the airglow is properly considered. The mesospheric variations due to gravity waves may intro-
duce extra uncertainty if unaccounted for, but little biases. However, the O2 column will be biased low by
∼10% if airglow is not retrieved.
Although the O2 (a1 Δg ) airglow is markedly strong (Figure 3), its spatial and spectral variations can be well
understood, and its spectral feature can be adequately separated from O2 absorption at the spectral resolution

SUN ET AL. 5785


Acknowledgments
K. Sun, X. Liu, and K. Chance
acknowledge support from the
Environmental Defense Fund (EDF-SAO
Grant dated 30 January 2018) and the
Smithsonian Institution. K. Sun
acknowledges support from School of
Engineering and Applied Sciences and
the RENEW Institute in University at
Buffalo. I. Gordon acknowledges
support through the NASA AURA (NNX
17AI78G) grant. We thank David Crisp at
JPL, Christian Frankenberg at Caltech,
Johannes Orphal and Miriam Sinnhuber
at KIT, Peter Cheimets and Jenna Samra
at the SAO, and Jonathan Franklin at
Harvard for helpful discussions. We
thank the European Space Agency for
supplying SCIAMACHY data at
https://earth.esa.int/web/guest/
-/sciamachy-localized-atmospheric-
spectra-in-the-uvvisnear-ir-wavelength-
range-1549, and the NASA MSIS team
for providing the MSIS results at
https://omniweb.gsfc.nasa.gov/vitmo/
msis_vitmo.html. HITRAN data are
available at http://www.hitran.org/.
MERRA-2 data are available at
https://gmao.gsfc.nasa.gov/reanalysis/
MERRA-2/data_access/.
SUN ET AL.
Geophysical Research Letters 10.1029/2018GL077823
of modern spaceborne spectrometers. An independent study by the MicroCarb team also draws similar con-
clusions (Jouglet et al., 2016). As such, we call on the greenhouse gas remote sensing community to reconsider
the O2 (a1 Δg ) band in future missions.
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