Vertical Profiles Of Trace Gases Research Articles

Stratospheric-trace-gas-profile retrievals from balloon-borne limb imaging of mid-infrared emission spectra

Abstract. The Limb Imaging Fourier Transform Spectrometer Experiment (LIFE) instrument is a balloon-borne prototype of a satellite instrument designed to take vertical images of atmospheric limb emission spectra in the 700–1400 cm−1 wavenumber range from the upper-troposphere–lower-stratosphere (UTLS) altitude region of the atmosphere. The prototype builds on the success of past and existing instruments while reducing the complexity of the imaging design. This paper details the results of a demonstration flight on a stabilized stratospheric balloon gondola from Timmins, Canada, in August 2019. Retrievals of vertical trace gas profiles for the important greenhouse gases H2O, O3, CH4, and N2O, as well as HNO3, are performed using an optimal estimation approach and the SASKTRAN radiative transfer model. The retrieved profiles are compared to approximately coincident observations made by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) solar occultation and Microwave Limb Sounder (MLS) instruments. An evaluation of the LIFE measurements is performed, and areas of improvement are identified. This work increases the overall technical readiness of the approach for future balloon, aircraft, and space applications.

Preflight Evaluation of the Environmental Trace Gases Monitoring Instrument with Nadir and Limb Modes (EMI-NL) Based on Measurements of Standard NO2 Sample Gas

Hyperspectral observations are used to retrieve high-resolution horizontal distribution and vertical profiles of trace gases (O3, NO2, HCHO, and SO2), thereby playing a vital role in monitoring the spatio-temporal distribution and transportation of atmospheric pollutants. These observations reflect air quality changes on global and regional scales, including China, thereby elucidating the impacts of anthropogenic and natural emissions on atmospheric composition and global climate change. The DaQi 02 (DQ02) satellite carries the Environmental Trace Gases Monitoring Instrument with Nadir and Limb modes (EMI-NL) onboard, which will simultaneously perform nadir and limb measurements of high-resolution ultraviolet and visible solar scattered light in the nadir and limb directions. Combined with the absorption of different trace gases in this wavelength band, this information can provide high-resolution horizontal and vertical distributions of trace gases. We examined the spectral measuring ability and instrument characteristics of both modules of EMI-NL by measuring different light sources and concentrations of the NO2 sample gas. In the nadir module test, when the NO2 sample gas concentration was 198 ppm and 513 ppm with scattered sunlight as the light source, the average relative errors of spatial pixels were 4.02% and 3.64%, respectively. At the NO2 sample gas concentration of 198 ppm with the integrating sphere as the light source, the average relative error of spatial pixels was −2.26%. In the limb module test, when the NO2 sample gas concentration was 198 ppm and 1000 ppm with the tungsten halogen lamp as the light source, the average relative errors of spatial pixels were −3.07% and 8.32%, respectively. When the NO2 sample gas concentration was 198 ppm and 1000 ppm with the integrating sphere as the light source, the spatial pixel average errors were −3.5% and 8.06%, respectively. The retrieved NO2 slant column density between different spatial pixels exhibited notable inconsistency in both modules, which could be used to estimate the stripe of spatial dimension. These results confirm the ability of EMI-NL to provide accurate spaceborne monitoring of NO2 globally.

Air quality observations onboard commercial and targeted Zeppelin flights in Germany – a platform for high-resolution trace-gas and aerosol measurements within the planetary boundary layer

Abstract. A Zeppelin airship was used as a platform for in situ measurements of greenhouse gases and short-lived air pollutants within the planetary boundary layer (PBL) in Germany. A novel quantum cascade laser-based multi-compound gas analyzer (MIRO Analytical AG) was deployed to simultaneously measure in situ concentrations of greenhouse gases (CO2, N2O, H2O, and CH4) and air pollutants (CO, NO, NO2, O3, SO2, and NH3) with high precision at a measurement rate of 1 Hz. These measurements were complemented by electrochemical sensors for NO, NO2, Ox (NO2 + O3), and CO, an optical particle counter, temperature, humidity, altitude, and position monitoring. Instruments were operated remotely without the need for on-site interactions. Three 2-week campaigns were conducted in 2020 comprising commercial passenger as well as targeted flights over multiple German cities including Cologne, Mönchengladbach, Düsseldorf, Aachen, Frankfurt, but also over industrial areas and highways. Vertical profiles of trace gases were obtained during the airship landing and take-off. Diurnal variability of the Zeppelin vertical profiles was compared to measurements from ground-based monitoring stations with a focus on nitrogen oxides and ozone. We find that their variability can be explained by the increasing nocturnal boundary layer height from early morning towards midday, an increase in emissions during rush hour traffic, and the rapid photochemical activity midday. Higher altitude (250–450 m) NOx to CO ratios are further compared to the 2015 EDGAR emission inventory to find that pollutant concentrations are influenced by transportation and residential emissions as well as manufacturing industries and construction activity. Finally, we report NOx and CO concentrations from one plume transect originating from a coal power plant and compare it to the EURopean Air pollution Dispersion-Inverse Modell (EURAD-IM) model to find agreement within 15 %. However, due to the increased contribution of solar and wind energy and the impact of lockdown measures the power plant was operating at max. 50 % capacity; therefore, possible overestimation of emissions by the model cannot be excluded.

Using atmospheric trace gas vertical profiles to evaluate model fluxes: a case study of Arctic-CAP observations and GEOS simulations for the ABoVE domain

Abstract. Accurate estimates of carbon–climate feedbacks require an independent means for evaluating surface flux models at regional scales. The altitude-integrated enhancement (AIE) derived from the Arctic Carbon Atmospheric Profiles (Arctic-CAP) project demonstrates the utility of this bulk quantity for surface flux model evaluation. This bulk quantity leverages background mole fraction values from the middle free troposphere, is agnostic to uncertainties in boundary layer height, and can be derived from model estimates of mole fractions and vertical gradients. To demonstrate the utility of the bulk quantity, six airborne profiling surveys of atmospheric carbon dioxide (CO2), methane (CH4), and carbon monoxide (CO) throughout Alaska and northwestern Canada between April and November 2017 were completed as part of NASA's Arctic–Boreal Vulnerability Experiment (ABoVE). The Arctic-CAP sampling strategy involved acquiring vertical profiles of CO2, CH4, and CO from the surface to 5 km altitude at 25 sites around the ABoVE domain on a 4- to 6-week time interval. All Arctic-CAP measurements were compared to a global simulation using the Goddard Earth Observing System (GEOS) modeling system. Comparisons of the AIE bulk quantity from aircraft observations and GEOS simulations of atmospheric CO2, CH4, and CO highlight the fidelity of the modeled surface fluxes. The model–data comparison over the ABoVE domain reveals that while current state-of-the-art models and flux estimates are able to capture broad-scale spatial and temporal patterns in near-surface CO2 and CH4 concentrations, more work is needed to resolve fine-scale flux features that are captured in CO observations.

Enhancing MAX-DOAS atmospheric state retrievals by multispectral polarimetry – studies using synthetic data

Abstract. Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) is a widely used measurement technique for the remote detection of atmospheric aerosol and trace gases. The technique relies on the analysis of ultra-violet and visible radiation spectra of scattered sunlight (skylight) to obtain information on different atmospheric parameters. From an appropriate set of spectra recorded under different viewing directions (typically a group of observations at different elevation angles) the retrieval of aerosol and trace gas vertical distributions is achieved through numerical inversion methods. It is well known that the polarisation state of skylight is particularly sensitive to atmospheric aerosol content as well as aerosol properties and that polarimetric measurements could therefore provide additional information for MAX-DOAS profile retrievals; however, such measurements have not yet been used for this purpose. To address this issue, we have developed the RAPSODI (Retrieval of Atmospheric Parameters from Spectroscopic Observations using DOAS Instruments) algorithm. In contrast to existing MAX-DOAS algorithms, it can process polarimetric information, and it can retrieve simultaneously profiles of aerosols and various trace gases at multiple wavelengths in a single retrieval step; a further advantage is that it contains a Mie scattering model, allowing for the retrieval of aerosol microphysical properties. The forward-model component in RAPSODI is based on a linearised vector radiative transfer model with Jacobian facilities, and we have used this model to create a database of synthetic measurements in order to carry out sensitivity analyses aimed at assessing the potential of polarimetric MAX-DOAS observations. We find that multispectral polarimetry significantly enhances the sensitivity, particularly to aerosol-related quantities. Assuming typical viewing geometries, the degrees of freedom for signal (DOFS) increase by about 50 % and 70 % for aerosol vertical distributions and aerosol properties, respectively, and by approximately 10 % for trace gas vertical profiles. For an idealised scenario with a horizontally homogeneous atmosphere, our findings predict an improvement in the inversion results' accuracy (root-mean-square deviations to the true values) of about 60 % for aerosol vertical column densities (VCDs) as well as for aerosol surface concentrations and by 40 % for aerosol properties. For trace gas VCDs, very little improvement is apparent, although the accuracy of trace gas surface concentrations improves by about 50 %.

Retrieval of tropospheric aerosol, NO<sub>2</sub>, and HCHO vertical profiles from MAX-DOAS observations over Thessaloniki, Greece: intercomparison and validation of two inversion algorithms

Abstract. In this study we focus on the retrieval of aerosol and trace gas vertical profiles from multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations for the first time over Thessaloniki, Greece. We use two independent inversion algorithms for the profile retrievals: the Mexican MAX-DOAS Fit (MMF) and the Mainz Profile Algorithm (MAPA). The former is based on the optimal estimation method (OEM), while the latter follows a parameterization approach. We evaluate the performance of MMF and MAPA, and we validate their retrieved products with ancillary data measured by other co-located reference instruments. The trace gas differential slant column densities (dSCDs), simulated by the forward models, are in good agreement, except for HCHO, where larger scatter is observed due to the increased spectral noise of the measurements in the UV. We find an excellent agreement between the tropospheric column densities of NO2 retrieved by MMF and MAPA (slope=1.009, Pearson's correlation coefficient R=0.982) and a good correlation for the case of HCHO (R=0.927). For aerosols, we find better agreement for the aerosol optical depths (AODs) in the visible (i.e., at 477 nm) compared to the UV (at 360 nm), and we show that the agreement strongly depends on the O4 scaling factor that is used in the analysis. The agreement for NO2 and HCHO near-surface concentrations is similar to the comparison of the integrated columns with slightly decreased correlation coefficients. The seasonal mean vertical profiles that are retrieved by MMF and MAPA are intercompared, and the seasonal variation in all species along with possible sources is discussed. The AODs retrieved by the MAX-DOAS are validated by comparing them with AOD values measured by a CIMEL sun photometer and a Brewer spectrophotometer. Four different flagging schemes were applied to the data in order to evaluate their performance. Qualitatively, a generally good agreement is observed for both wavelengths, but we find a systematic bias from the CIMEL sun photometer and Brewer spectrophotometer measurements, due to the limited sensitivity of the MAX-DOAS in retrieving information at higher altitudes, especially in the UV. An in-depth validation of the aerosol vertical profiles retrieved by the MAX-DOAS is not possible since only in very few cases is the true aerosol profile known during the period of study. However, we examine four cases, where the MAX-DOAS provided a generally good estimation of the shape of the profiles retrieved by a co-located multi-wavelength lidar system. The NO2 near-surface concentrations are validated against in situ observations, and the comparison of both MMF and MAPA revealed good agreement with correlation coefficients of R=0.78 and R=0.73, respectively. Finally, the effect of the O4 scaling factor is investigated by intercomparing the integrated columns retrieved by the two algorithms and also by comparing the AODs derived by MAPA for different values of the scaling factor with AODs measured by the CIMEL sun photometer and the Brewer spectrophotometer.

Simulated multispectral temperature and atmospheric composition retrievals for the JPL GEO-IR Sounder

Abstract. Satellite measurements enable quantification of atmospheric temperature, humidity, wind fields, and trace gas vertical profiles. The majority of current instruments operate on polar orbiting satellites and either in the thermal and mid-wave or in the shortwave infrared spectral regions. We present a new multispectral instrument concept for improved measurements from geostationary orbit (GEO) with sensitivity to the boundary layer. The JPL GEO-IR Sounder, which is an imaging Fourier transform spectrometer, uses a wide spectral range (1–15.4 µm) encompassing both reflected solar and thermal emission bands to improve sensitivity to the lower troposphere and boundary layer. We perform retrieval simulations for both clean and polluted scenarios that also encompass different temperature and humidity profiles. The results illustrate the benefits of combining shortwave and thermal infrared measurements. In particular, the former adds information in the boundary layer, while the latter helps to separate near-surface and mid-tropospheric variability. The performance of the JPL GEO-IR Sounder is similar to or better than currently operational instruments. The proposed concept is expected to improve weather forecasting as well as severe storm tracking and forecasting and also benefit local and global air quality and climate research.

Technical note: Evaluation of profile retrievals of aerosols and trace gases for MAX-DOAS measurements under different aerosol scenarios based on radiative transfer simulations

Abstract. Ground-based Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) is a state-of-the-art remote sensing technique for deriving vertical profiles of trace gases and aerosols. However, MAX-DOAS profile inversions under aerosol pollution scenarios are challenging because of the complex radiative transfer and limited information content of the measurements. In this study, the performances of two inversion algorithms were evaluated for various aerosol pollution scenarios based on synthetic slant column densities (SCDs) derived from radiative transfer simulations. Compared to previous studies, in our study, much larger ranges of aerosol optical depth (AOD) and NO2 vertical column densities (VCDs) are covered. One inversion algorithm is based on optimal estimation; the other uses a parameterized approach. In this analysis, three types of profile shapes for aerosols and NO2 were considered: exponential, Boltzmann, and Gaussian. First, the systematic deviations of the retrieved aerosol profiles from the input profiles were investigated. For most cases, the AODs of the retrieved profiles were found to be systematically lower than the input values, and the deviations increased with increasing AOD. In particular for the optimal estimation algorithm and for high AOD, these findings are consistent with the results in previous studies. The assumed single scattering albedo (SSA) and asymmetry parameter (AP) have a systematic influence on the aerosol retrieval. However, for most cases the influence of the assumed SSA and AP on the retrieval results are rather small (compared to other uncertainties). For the optimal estimation algorithm, the agreement with the input values can be improved by optimizing the covariance matrix of the a priori uncertainties. Second, the aerosol effects on the NO2 profile retrieval were tested. Here, especially for the optimal estimation algorithm, a systematic dependence on the NO2 VCD was found, with a strong relative overestimation of the retrieved results for low NO2 VCDs and an underestimation for high NO2 VCDs. In contrast, the dependence on the aerosol profiles was found to be rather low. Interestingly, the results for both investigated wavelengths (360 and 477 nm) were found to be rather similar, indicating that the differences in the radiative transfer between both wavelengths have no strong effect. In general, both inversion schemes can retrieve the near-surface values of aerosol extinction and trace gas concentrations well.

Vertical profiles of trace gas and aerosol properties over the eastern North Atlantic: variations with season and synoptic condition

Abstract. Because of their extensive coverage, marine low clouds greatly impact the global climate. Presently, the response of marine low clouds to the changes in atmospheric aerosols remains a major source of uncertainty in climate simulations. One key contribution to this large uncertainty derives from the poor understanding of the properties and processes of marine aerosols under natural conditions and the perturbation by anthropogenic emissions. The eastern North Atlantic (ENA) is a region of persistent but diverse subtropical marine boundary layer (MBL) clouds, where cloud albedo and precipitation are highly susceptible to perturbations in aerosol properties. Here we examine the key processes that drive the cloud condensation nuclei (CCN) population in the MBL using comprehensive characterizations of aerosol and trace gas vertical profiles during the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) field campaign. During ACE-ENA, a total of 39 research flights were conducted in the Azores: 20 during summer 2017 and 19 during winter 2018. During summer, long-range-transported aerosol layers were periodically observed in the lower free troposphere (FT), leading to elevated FT CCN concentrations (NCCN). Both biomass burning and pollution from North America contribute to submicron aerosol mass in these layers, with pollution likely the dominant contributor. In contrast, long-range transported continental emissions have a much weaker influence on the aerosol properties in the ENA during the winter season. While the entrainment of FT air is a major source of particle number in the MBL for both seasons, on average it does not serve as a direct source of CCN in the MBL because the average FT NCCN is the same or even lower than that in the MBL. The particle number flux due to FT entrainment is dominated by pre-CCN (particles that are too small to form cloud droplets under typical conditions, i.e., particles with sizes below the Hoppel minimum) due to the elevated Npre-CCN in the lower FT. Once these pre-CCN are entrained into the MBL, they can grow and reach CCN size range through condensational growth, representing an indirect and major source of MBL CCN in the ENA. The impact of synoptic conditions on the aerosol properties is examined. Under pre-front and post-front conditions, shallow convective activity often leads to a deep and decoupled boundary layer. Coalescence scavenging and evaporation of drizzle below clouds lead to reduced NCCN and larger accumulation-mode particle sizes in the upper cloud-containing decoupled layer, indicating that surface measurements overestimate the NCCN relevant to the formation of MBL clouds under decoupled conditions.

Long-term MAX-DOAS measurements of NO<sub>2</sub>, HCHO, and aerosols and evaluation of corresponding satellite data products over Mohali in the Indo-Gangetic Plain

Abstract. We present comprehensive long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of aerosols, nitrogen dioxide (NO2), and formaldehyde (HCHO) from Mohali (30.667∘ N, 76.739∘ E; ∼310 m above mean sea level), located in the densely populated Indo-Gangetic Plain (IGP) of India. We investigate the temporal variation in tropospheric columns, surface volume mixing ratio (VMR), and vertical profiles of aerosols, NO2, and HCHO and identify factors driving their ambient levels and distributions for the period from January 2013 to June 2017. We observed mean aerosol optical depth (AOD) at 360 nm, tropospheric NO2 vertical column density (VCD), and tropospheric HCHO VCD for the measurement period to be 0.63 ± 0.51, (6.7 ± 4.1) × 1015, and (12.1 ± 7.5) × 1015 molecules cm−2, respectively. Concerning the tropospheric NO2 VCDs, Mohali was found to be less polluted than urban and suburban locations of China and western countries, but comparable HCHO VCDs were observed. For the more than 4 years of measurements during which the region around the measurement location underwent significant urban development, we did not observe obvious annual trends in AOD, NO2, and HCHO. High tropospheric NO2 VCDs were observed in periods with enhanced biomass and biofuel combustion (e.g. agricultural residue burning and domestic burning for heating). Highest tropospheric HCHO VCDs were observed in agricultural residue burning periods with favourable meteorological conditions for photochemical formation, which in previous studies have shown an implication for high ambient ozone also over the IGP. Highest AOD is observed in the monsoon season, indicating possible hygroscopic growth of the aerosol particles. Most of the NO2 is located close to the surface, whereas significant HCHO is present at higher altitudes up to 600 m during summer indicating active photochemistry at high altitudes. The vertical distribution of aerosol, NO2, and HCHO follows the change in boundary layer height (BLH), from the ERA5 dataset of European Centre for Medium-Range Weather Forecasts, between summer and winter. However, deep convection during the monsoon transports the pollutants at high altitudes similar to summer despite a shallow ERA5 BLH. Strong gradients in the vertical profiles of HCHO are observed during the months when primary anthropogenic sources dominate the formaldehyde production. High-resolution MODIS AOD measurements correlate well but were systematically higher than MAX-DOAS AODs. The ground-based MAX-DOAS measurements were used to evaluate three NO2 data products and two HCHO data products of the Ozone Monitoring Instrument (OMI) for the first time over India and the IGP. NO2 VCDs from OMI correlate reasonably with MAX-DOAS VCDs but are lower by ∼30 %–50 % due to the difference in vertical sensitivities and the rather large OMI footprint. OMI HCHO VCDs exceed the MAX-DOAS VCDs by up to 30 %. We show that there is significant scope for improvement in the a priori vertical profiles of trace gases, which are used in OMI retrievals. The difference in vertical representativeness was found to be crucial for the observed biases in NO2 and HCHO surface VMR intercomparisons. Using the ratio of NO2 and HCHO VCDs measured from MAX-DOAS, we have found that the peak daytime ozone production regime is sensitive to both NOx and VOCs in winter but strongly sensitive to NOx in other seasons.

Intercomparison of MAX-DOAS vertical profile retrieval algorithms: studies using synthetic data

Abstract. Multi-axis differential optical absorption spectroscopy (MAX-DOAS) is a widely used measurement technique for the detection of a variety of atmospheric trace gases. Using inverse modelling, the observation of trace gas column densities along different lines of sight enables the retrieval of aerosol and trace gas vertical profiles in the atmospheric boundary layer using appropriate retrieval algorithms. In this study, the ability of eight profile retrieval algorithms to reconstruct vertical profiles is assessed on the basis of synthetic measurements. Five of the algorithms are based on the optimal estimation method, two on parametrised approaches, and one using an analytical approach without involving any radiative transfer modelling. The synthetic measurements consist of the median of simulated slant column densities of O4 at 360 and 477 nm, as well as of HCHO at 343 nm and NO2 at 477 nm, from seven datasets simulated by five different radiative transfer models. Simulations are performed for a combination of 10 trace gas and 11 aerosol profiles, as well as 11 elevation angles, three solar zenith, and three relative azimuth angles. Overall, the results from the different algorithms show moderate to good performance for the retrieval of vertical profiles, surface concentrations, and total columns. Except for some outliers, the root-mean-square difference between the true and retrieved state ranges between (0.05–0.1) km−1 for aerosol extinction and (2.5–5.0) ×1010 molec cm−3 for HCHO and NO2 concentrations.

Vertical Profiles of Tropospheric Ozone From MAX‐DOAS Measurements During the CINDI‐2 Campaign: Part 1—Development of a New Retrieval Algorithm

AbstractGround‐based measurements of tropospheric ozone (O3) are valuable for studies of atmospheric chemistry, air pollution, climate change, and for satellite validation. The Multi Axis Differential Optical Absorption Spectroscopy (MAX‐DOAS) technique has been widely used to derive vertical profiles of trace gases and aerosols in the troposphere. However, tropospheric O3 has not yet been satisfactorily derived from MAX‐DOAS measurements due to the influence of stratospheric O3 absorption. In this study, we developed two new retrieval approaches for tropospheric O3 from MAX‐DOAS measurements. In method 1, stratospheric O3 profiles from external data sources are considered in the retrieval. In method 2, stratospheric and tropospheric O3 are separated based on the temperature‐dependent differences between tropospheric and stratospheric O3 absorption structures in the UV spectral range. The feasibility of both methods is first verified by applying them to synthetic spectra. Then they are applied to real MAX‐DOAS measurements recorded during the CINDI‐2 campaign in Cabauw, the Netherlands (September 2016). The obtained results are compared with independent O3 measurements and global chemical transport model simulations. Good agreement of the near‐surface O3 concentrations with the independent data sets is found for both methods. However, tropospheric O3 profiles are only reasonably derived using method 1, while they are significantly overestimated at altitudes above 1 km using method 2, probably due to the approximation of the ring spectra used to correct the rotational Raman scattering structures in the DOAS fit. Advantages and disadvantages of both methods are discussed and improvement directions are suggested for further studies.

New temperature and pressure retrieval algorithm for high-resolution infrared solar occultation spectroscopy: analysis and validation against ACE-FTS and COSMIC

Abstract. Motivated by the initial selection of a high-resolution solar occultation Fourier transform spectrometer (FTS) to fly to Mars on the ExoMars Trace Gas Orbiter, we have been developing algorithms for retrieving volume mixing ratio vertical profiles of trace gases, the primary component of which is a new algorithm and software for retrieving vertical profiles of temperature and pressure from the spectra. In contrast to Earth-observing instruments, which can rely on accurate meteorological models, a priori information, and spacecraft position, Mars retrievals require a method with minimal reliance on such data. The temperature and pressure retrieval algorithms developed for this work were evaluated using Earth-observing spectra from the Atmospheric Chemistry Experiment (ACE) FTS, a solar occultation instrument in orbit since 2003, and the basis for the instrument selected for a Mars mission. ACE-FTS makes multiple measurements during an occultation, separated in altitude by 1.5–5 km, and we analyse 10 CO2 vibration–rotation bands at each altitude, each with a different usable altitude range. We describe the algorithms and present results of their application and their comparison to the ACE-FTS data products. The Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC) provides vertical profiles of temperature up to 40 km with high vertical resolution. Using six satellites and GPS radio occultation, COSMIC's data product has excellent temporal and spatial coverage, allowing us to find coincident measurements with ACE with very tight criteria: less than 1.5 h and 150 km. We present an intercomparison of temperature profiles retrieved from ACE-FTS using our algorithm, that of the ACE Science Team (v3.5), and from COSMIC. When our retrievals are compared to ACE-FTS v3.5, we find mean differences between −5 and +2 K and that our retrieved profiles have no seasonal or zonal biases but do have a warm bias in the stratosphere and a cold bias in the mesosphere. When compared to COSMIC, we do not observe a warm/cool bias and mean differences are between −4 and +1 K. COSMIC comparisons are restricted to below 40 km, where our retrievals have the best agreement with ACE-FTS v3.5. When comparing ACE-FTS v3.5 to COSMIC we observe a cold bias in COSMIC of 0.5 K, and mean differences are between −0.9 and +0.6 K.

Simulation of source intensity variations from atmospheric dust for solar occultation Fourier transform infrared spectroscopy at Mars

A Fourier transform spectrometer observing in solar occultation mode from orbit is ideally suited to detecting and characterizing vertical profiles of trace gases in the Martian atmosphere. This technique benefits from a long optical path length and high signal strength, and can have high spectral resolution. The Martian atmosphere is often subject to large quantities of suspended dust, which attenuates solar radiation along the line-of-sight. An instrument making solar occultation measurements scans the limb of the atmosphere continuously, and the optical path moves through layers of increasing or decreasing dust levels during a single interferogram acquisition, resulting in time-varying signal intensity. If uncorrected, source intensity variations (SIVs) can affect the relative depth of absorption lines, negatively impacting trace gas retrievals. We have simulated SIVs using synthetic spectra for the Martian atmosphere, and investigated different techniques to mitigate the effects of SIVs. We examined high-pass filters in the wavenumber domain, and smoothing methods in the optical path difference (OPD) domain, and conclude that using a convolution operator in the OPD domain can isolate the SIVs and be used to correct for it. We observe spectral residuals of less than 0.25% in both high- and low-dust conditions, and retrieved volume mixing ratio vertical profile differences on the order of 0.5–3% for several trace gases known to be present in the Martian atmosphere. These differences are smaller than those caused by adding realistic noise to the spectra. This work thus demonstrates that it should be possible to retrieve vertical profiles of trace gases in a dusty Martian atmosphere using solar occultation if the interferograms are corrected for the effects of dust.

The CU 2-D-MAX-DOAS instrument – Part 1: Retrieval of 3-D distributions of NO<sub>2</sub> and azimuth-dependent OVOC ratios

Abstract. We present an innovative instrument telescope and describe a retrieval method to probe three-dimensional (3-D) distributions of atmospheric trace gases that are relevant to air pollution and tropospheric chemistry. The University of Colorado (CU) two-dimensional (2-D) multi-axis differential optical absorption spectroscopy (CU 2-D-MAX-DOAS) instrument measures nitrogen dioxide (NO2), formaldehyde (HCHO), glyoxal (CHOCHO), oxygen dimer (O2–O2, or O4), and water vapor (H2O); nitrous acid (HONO), bromine monoxide (BrO), and iodine monoxide (IO) are among other gases that can in principle be measured. Information about aerosols is derived through coupling with a radiative transfer model (RTM). The 2-D telescope has three modes of operation: mode 1 measures solar scattered photons from any pair of elevation angle (−20° < EA < +90° or zenith; zero is to the horizon) and azimuth angle (−180° < AA < +180°; zero being north); mode 2 measures any set of azimuth angles (AAs) at constant elevation angle (EA) (almucantar scans); and mode 3 tracks the direct solar beam via a separate view port. Vertical profiles of trace gases are measured and used to estimate mixing layer height (MLH). Horizontal distributions are then derived using MLH and parameterization of RTM (Sinreich et al., 2013). NO2 is evaluated at different wavelengths (350, 450, and 560 nm), exploiting the fact that the effective path length varies systematically with wavelength. The area probed is constrained by O4 observations at nearby wavelengths and has a diurnal mean effective radius of 7.0 to 25 km around the instrument location; i.e., up to 1960 km2 can be sampled with high time resolution. The instrument was deployed as part of the Multi-Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) in Mainz, Germany, from 7 June to 6 July 2013. We present first measurements (modes 1 and 2 only) and describe a four-step retrieval to derive (a) boundary layer vertical profiles and MLH of NO2; (b) near-surface horizontal distributions of NO2; (c) range-resolved NO2 horizontal distribution measurements using an "onion-peeling" approach; and (d) the ratios HCHO to NO2 (RFN), CHOCHO to NO2 (RGN), and CHOCHO to HCHO (RGF) at 14 pre-set azimuth angles distributed over a 360° view. Three-dimensional distribution measurements with 2-D-MAX-DOAS provide an innovative, regional perspective of trace gases as well as their spatial and temporal concentration gradients, and they maximize information to compare near-surface observations with atmospheric models and satellites.

Remote sensing measurements of the CO2 mixing ratio in the planetary boundary layer using cloud slicing with airborne lidar

AbstractWe have measured the CO2 volume mixing ratio (VMR) within the planetary boundary layer (PBL) using cloud slicing with an airborne pulsed integrated path differential absorption (IPDA) lidar from flight altitudes of up to 13 km. During a flight over Iowa in summer 2011, simultaneous measurement of the optical range and CO2 absorption to clouds and the ground were made using time‐resolved detection of pulse echoes from each scattering surface. We determined the CO2 absorption in the PBL by differencing the two lidar‐measured absorption line shapes, one to a broken shallow cumulus cloud layer located at the top of the PBL and the other to the ground. Solving for the CO2 VMR in the PBL and that of the free troposphere, we measured a ≈15 ppm (4%) drawdown in the PBL. Both CO2 VMRs were within ≈3 ppm of in situ CO2 profile measurements. We have also demonstrated cloud slicing using scatter from thin, diffuse cirrus clouds and cumulus clouds, which allowed solving for the CO2 VMR for three vertical layers. The technique and retrieval algorithm are applicable to a space‐based lidar instrument as well as to lidar IPDA measurements of other trace gases. Thus, lidar cloud slicing also offers promise toward space‐based remote sensing of vertical trace gas profiles in the atmosphere using a variety of clouds.

Microcollection of Gases in a Capillary Tube: Preservation of Spatial and Temporal Resolution

Researchers at the National Oceanic and Atmospheric Administration (NOAA) have recently developed and reported a novel air collection device for measuring vertical profiles of trace gases in the atmosphere, which has been applied to carbon dioxide and methane so far. The device consists of a long stainless steel tube that is prefilled with calibrated gas and allowed to ascend on a weather balloon. During ascent, the device is evacuated as it equilibrates with the decreasing atmospheric pressure. During descent, the tube is filled with atmospheric gas in an ordered manner. The diffusion rate inside the tube is slow enough that the collected gas remains ordered. Here is reported a miniaturization of the device described above, in which the stainless steel tube is replaced with Hydroguard fused silica tubing (0.53 mm × 30 m) and two lightweight valves having a total mass of less than 28 g. This micro-AirCore device was deployed on the SwRI-developed unmanned SkyWisp glider. Profiling of carbon dioxide in the atmosphere proceeded via mass spectrometric detection. A laboratory-based validation system was used for evaluating the micro-AirCore function, including accuracy and precision, for carbon dioxide. The diffusion profiles of carbon dioxide, argon, oxygen, and methane were also investigated. Overall, the micro-AirCore demonstrated an accuracy error of 2% ((12)CO(2)) and minimal diffusion over a period of 16 h (peak width increased by a factor of 1.6). Even after 63 h, mixing of the gases inside the tube was not complete. A triplet of micro-AirCores was deployed on the SkyWisp glider yielding a relative standard deviation of 0.08%, or 0.3 ppm, for CO(2). The profile collected resulted in observation of the boundary layer with elevated CO(2) levels, a region in the free troposphere with relatively constant CO(2) mole fraction, and a gradual decrease in CO(2) above 10,000 m. This microdevice has broad applications extending beyond vertical profiling. Fitting the device with a metering device could enable horizontal collection of gases.

CRISTA-NF measurements with unprecedented vertical resolution during the RECONCILE aircraft campaign

Abstract. The Cryogenic Infrared Spectrometers and Telescope for the Atmosphere – New Frontiers (CRISTA-NF), an airborne infrared limb-sounder, was operated aboard the high-flying Russian research aircraft M55-Geophysica during the Arctic RECONCILE campaign from January to March 2010. This paper describes the calibration process of the instrument and the retrieval algorithm employed and then proceeds to present retrieved trace gas volume mixing ratio cross-sections for one specific flight in this campaign. We are able to resolve the uppermost troposphere/lower stratosphere for several trace gas species for several kilometres below the flight altitude (16 to 19 km) with an unprecedented vertical resolution of 400 to 500 m for the limb-sounding technique. The instrument points sideways with respect to the flight direction. Therefore, the observations are also characterised by a rather high horizontal sampling along the flight track, which provides a full vertical profile every ≈15 km. Assembling the vertical trace gas profiles derived from CRISTA-NF measurements to cross-sections shows filaments of vortex and extra-vortex air masses in the vicinity of the polar vortex. During this campaign, the M55-Geophysica carried further instruments enabling trace gas volume mixing ratios derived from CRISTA-NF to be validated by comparing them with measurements by the in situ instruments HAGAR and FOZAN and observations by MIPAS-STR. This validation suggests that the retrieved trace gas volume mixing ratios are both qualitatively and quantitatively reliable.

The NIMO Monte Carlo model for box-air-mass factor and radiance calculations

A new fully spherical multiple scattering Monte Carlo radiative transfer model named NIMO (NIWA Monte Carlo model) is presented. The ray tracing algorithm is described in detail along with the treatment of scattering and absorption, and the simulation of backward adjoint trajectories. The primary application of NIMO is the calculation of box-air-mass factors (box-AMFs), which are used to convert slant column densities (SCDs) of trace gases, derived from UV–visible multiple axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements, into vertical column densities (VCDs). Box-AMFs are also employed as weighting functions for optimal estimation retrievals of vertical trace gas profiles from SCDs. Monte Carlo models are well suited to AMF calculations at high solar zenith angles (SZA) and at low viewing elevation angles where multiple scattering is important. Additionally, the object-oriented structure of NIMO makes it easily extensible to new applications by plugging in objects for new absorbing or scattering species. Box-AMFs and radiances, calculated for various wavelengths, SZAs, viewing elevation and azimuth angles and aerosol scenarios, are compared with results from nine other models using a set of exercises from a recent radiative transfer model intercomparison. NIMO results for these simulations are well within the range of variability of the other models.

Multiple wavelength retrieval of tropospheric aerosol optical properties from MAXDOAS measurements in Beijing

Abstract. We report on the retrieval of aerosol extinction profiles at four wavelengths from ground-based multi-axis differential absorption spectroscopy (MAXDOAS) measurements performed in Beijing, China. Measurements were made over a 10-month time period (June 2008 to April 2009) using a newly developed MAXDOAS instrument. A retrieval algorithm, based on an on-line implementation of the radiative transfer code LIDORT and the optimal estimation technique, has been designed to provide near real time information on aerosol extinction vertical profiles. The algorithm was applied to O4 measurements at four wavelengths (360, 477, 577, and 630 nm). The total aerosol optical depths (AODs) calculated from the retrieved profiles exhibit higher values in spring and summer and lower values in autumn and winter. Comparison of the retrieved total AODs with values from a co-located CIMEL sunphotometer revealed a good correlation. The best results are obtained for the UV region with a correlation coefficient (R) of 0.91 and a slope of the linear regression fit of 1.1. At the longest wavelength, R drops down to 0.67 and the slope increases to 1.5. The results confirm that good quality O4 slant column measurements are essential for the success of the retrievals. A method is presented to determine a correction factor to account for systematic errors. It is demonstrated that the algorithm is capable of reliably retrieving aerosol extinction profiles for a wide range of atmospheric conditions (total AODs at 360 nm ranging from about 0.1 to 3). The results open up new perspectives for the extension of the algorithm for the near real time retrieval of trace gas vertical profiles.