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An all-fiber coupled laser heterodyne radiometer (LHR), using a wideband tunable external cavity diode laser (1500–1640 nm) as local oscillator laser, was developed for ground-based remote sensing of carbon dioxide. Optimal absorption lines and transmission spectra of carbon dioxide in this wavelength range were determined. High sensitivity of the LHR was achieved by using a balanced photodetector to suppress the relative intensity noise of the local oscillator laser. The noise model of the highly sensitive LHR was analyzed and compared with the traditional LHR using single photodetector [1-2]. Finally, field campaigns were performed on the roof of the platform of IRENE building in Dunkerque (51.05°N/2.34°E). The measured LHR spectra in the atmospheric column are compared, in good agreement, with referenced Fourier-transform infrared spectra from the TCCON observation network and with the simulation spectra resulting from an atmospheric transmission modeling. Experimental details including noise analysis and LHR spectra will be discussed and presented. AcknowledgmentsThe authors thank the financial supports from the LABEX CaPPA project (ANR-10-LABX005), the CPER ECRIN program, the EU H2020-ATMOS project as well as the funding from China Scholarship Council (CSC). References[1] T. G. Blaney. "Signal-to-noise ratio and other characteristics of heterodyne radiation receivers", Space Science Reviews 17 (1975) 691-702.[2] F. Shen, G. Wang, J. Wang, T. Tan, G. Wang, P. Jeseck, Y.-V. Te, X. Gao, W. Chen. "A transportable mid-infrared laser heterodyne radiometer operating in the shot-noise dominated regime", Opt. Lett.46 (2021) 3171-3174.

Anomalies of tropospheric columns of ozone (O$_3$), carbon monoxide (CO), acetylene (C$_2$H$_2$), formaldehyde (H$_2$CO), and ethane (C$_2$H$_6$) are quantified during the 2020 stringent COVID-19 world-wide lockdown using multiple ground-based Fourier-transform infrared spectrometers covering urban and remote conditions. We applied an exponential smoothing forecasting approach to the data sets to estimate business-as-usual values for 2020, which are then contrasted with actual observations. The Community Atmosphere Model with chemistry (CAM-chem) is used to simulate the same gases using lockdown-adjusted and business-as-usual emissions. The role of meteorology, or natural variability, is assessed with additional CAM-chem simulations. The tropospheric column of O$_3$ declined between March and May 2020 for most sites with a mean decrease of 9.2% ± 4.7%. Simulations reproduce these anomalies, especially under background conditions where natural variability explains up to 80% of the decline for sites in the Northern Hemisphere. While urban sites show a reduction between 1% and 12% in tropospheric CO, the remote sites do not show a significant change. Overall, CAM-chem simulations capture the magnitude of the anomalies and in many cases natural variability and lockdowns have opposite effects. We further used the long-term record of the Measurements of Pollution in the Troposphere (MOPITT) satellite instrument to capture global anomalies of CO. Reductions of CO vary highly across regions but North America and Europe registered lower values in March 2020. The absence of CO reduction in April and May, concomitant with reductions of anthropogenic emissions, is explained by a negative anomaly in the hydroxyl radical (OH) found with CAM-chem. The implications of these findings are discussed for methane (CH$_4$), which shows a positive lifetime anomaly during the COVID-19 lockdown period. The fossil fuel combustion by-product tracer C2H2 shows a mean drop of 13.6% ± 8.3% in urban Northern Hemisphere sites due to the reduction in emissions and in some sites exacerbated by natural variability. For some sites with anthropogenic influence there is a decrease in C$_2$H$_6$. The simulations capture the anomalies but the main cause may be related to natural variability. H$_2$CO declined during the stringent 2020 lockdown in all urban sites explained by reductions in emissions of precursors.

Carbonyl sulfide (OCS) is a non-hygroscopic trace species in the free troposphere and a large sulfur reservoir maintained by both direct oceanic, geologic, biogenic, and anthropogenic emissions and the oxidation of other sulfur-containing source species. It is the largest source of sulfur transported to the stratosphere during volcanically quiescent periods. Data from 22 ground-based globally dispersed stations are used to derive trends in total and partial column OCS. Middle infrared spectral data are recorded by solar-viewing Fourier transform interferometers that are operated as part of the Network for the Detection of Atmospheric Composition Change between 1986 and 2020. Vertical information in the retrieved profiles provides analysis of discreet altitudinal regions. Trends are found to have well-defined inflection points. NASA | Science Mission Directorate (SMD). Grant Numbers: NNX17AE38 G S003, 80NSSC21K0891. Natural Sciences and Engineering Research Council of Canada (NSERC); the Canadian Space Agency (CSA); Environment and Climate Change Canada (ECCC); Sorbonne Université; French Research Center CNRS; French Space Agency CNES. F.R.S.-FNRS. Grant Numbers: J.0147.18, J.0126.21. CONACYT. Grant Number: 290589. PAPIIT. Grant Number: IN111521. NIWA; New Zealand’s Ministry of Business, Innovation and Employment Strategic Science Investment Fund German research foundation. Grant Number: 268020496 German Bundesministerium für Wirtschaft und Energie (BMWi). Grant Numbers: 50EE1711A, 50EE1711D. Helmholtz Society Australian Research Council. Université de La Réunion. Grant Numbers: LACy-UMR8105, UMS3365.

Development of laser heterodyne radiometers operating in the near-IR near 1.5 µm and in the mid-IR near 8 µm for the measurements of CH4, N2O, 13CO2/12CO2, H2O/HDO vapor in the atmospheric column.

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Carbonyl sulfide (OCS) is a non-hygroscopic trace species in the free troposphere and the primary sulfur reservoir maintained by direct oceanic, geologic, biogenic and anthropogenic emissions and t...

A transportable laser heterodyne radiometer (LHR) based on an external cavity quantum cascade laser, operating in the mid-infrared (mid-IR) around 8 µm, was developed for ground-based remote sensing of multiple greenhouse gases. A newly available novel flexible mid-IR polycrystalline fiber was first exploited to couple solar radiation, real-time captured using a portable sun-tracker, to the LHR receiver. Compared to free space coupling of sunlight, the technique usually used nowadays in the mid-IR, such fiber coupling configuration makes the LHR system readily more stable, simpler, and robust. Operation of the LHR with quasi-shot-noise limited performance was analyzed and experimentally achieved by optimizing local oscillator power. To the best of our knowledge, no such performance approaching the fundamental limit has been reported for a transportable LHR operating at a long mid-IR wavelength around 8 µm. C H 4 and N 2 O were simultaneously measured in the atmospheric column using the developed mid-IR LHR. The experimental LHR spectrum of C H 4 and N 2 O was compared and is in good agreement with a referenced Fourier-transform infrared spectrum from the Total Carbon Column Observing Network observation site and with a simulation spectrum from atmospheric transmission modeling.

Observations of carbon monoxide (CO) from the Measurements Of Pollution In The Troposphere (MOPITT) instrument aboard the Terra spacecraft were expected to have an accuracy of 10 % prior to the launch in 1999. Here we evaluate MOPITT Version 7 joint (V7J) thermal-infrared and near-infrared (TIR–NIR) retrieval accuracy and precision and suggest ways to further improve the accuracy of the observations. We take five steps involving filtering or bias corrections to reduce scatter and bias in the data relative to other MOPITT soundings and ground-based measurements. (1) We apply a preliminary filtering scheme in which measurements over snow and ice are removed. (2) We find a systematic pairwise bias among the four MOPITT along-track detectors (pixels) on the order of 3–4 ppb with a small temporal trend, which we remove on a global scale using a temporally trended bias correction. (3) Using a small-region approximation (SRA), a new filtering scheme is developed and applied based on additional quality indicators such as the signal-to-noise ratio (SNR). After applying these new filters, the root-mean-squared error computed using the local median from the SRA over 16 years of global observations decreases from 3.84 to 2.55 ppb. (4) We also use the SRA to find variability in MOPITT retrieval anomalies that relates to retrieval parameters. We apply a bias correction to one parameter from this analysis. (5) After applying the previous bias corrections and filtering, we compare the MOPITT results with the GGG2014 ground-based Total Carbon Column Observing Network (TCCON) observations to obtain an overall global bias correction. These comparisons show that MOPITT V7J is biased high by about 6 %–8 %, which is similar to past studies using independent validation datasets on V6J. When using TCCON spectrometric column retrievals without the standard airmass correction or scaling to aircraft (WMO scale), the ground- and satellite-based observations overall agree to better than 0.5 %. GEOS-Chem data assimilations are used to estimate the influence of filtering and scaling to TCCON on global CO and tend to pull concentrations away from the prior fluxes and closer to the truth. We conclude with suggestions for further improving the MOPITT data products.

Electronic excitations near the surface of water ice lead to the desorption of adsorbed molecules, through a so far debated mechanism. A systematic study of photon-induced indirect desorption, revealed by the spectral dependence of the desorption (7 to 13 eV), is conducted for Ar, Kr, N2, and CO adsorbed on H2O or D2O amorphous ices. The mass and isotopic dependence and the increase of intrinsic desorption efficiency with photon energy all point to a mechanism of desorption induced by collisions between adsorbates and energetic H or D atoms, produced by photodissociation of water. This constitutes a direct and unambiguous experimental demonstration of the mechanism of indirect desorption of weakly adsorbed species on water ice, and sheds new light on the possibility of this mechanism in other systems. It also has implications for the description of photon-induced desorption in astrochemical models., Comment: Supplemental Material available freely at https://journals.aps.org/prl/supplemental/10.1103/PhysRevLett.126.156001

We report an investigation of X-ray induced desorption of neutrals, cations and anions from CO ice. The desorption of neutral CO, by far the most abundant, is quantified and discussed within the context of its application to astrochemistry. The desorption of many different cations, including large cations up to the mass limit of the spectrometer, are observed. In contrast, the only desorbing anions detected are O$^-$ and C$^-$. The desorption mechanisms of all these species are discussed with the aid of their photodesorption spectrum. The evolution of the X-ray absorption spectrum shows significant chemical modifications of the ice upon irradiation, which along with the desorption of large cations gives a new insight into X-ray induced photochemistry in CO ice., Comment: Accepted in PCCP

Vacuum-UV (VUV) photodesorption from water-rich ice mantles coating interstellar grains is known to play an important role in the gas-to-ice ratio in star- and planet-forming regions. Quantitative photodesorption yields from water ice are crucial for astrochemical models. We aim to provide the first quantitative photon-energy dependent photodesorption yields from water ice in the VUV. This information is important to understand the photodesorption mechanisms and to account for the variation of the yields under interstellar irradiation conditions. Experiments have been performed on the DESIRS beamline at the SOLEIL synchrotron, delivering tunable VUV light, using the SPICES (Surface Processes and ICES) set-up. Compact amorphous solid water ice (H$_2$O and D$_2$O) has been irradiated from 7 to 13.5 eV. Quantitative yields have been obtained by detection in the gas phase with mass-spectrometry for sample temperatures ranging from 15 K to 100 K. Photodesorption spectra of H$_2$O (D$_2$O), OH (OD), H$_2$ (D$_2$) and O$_2$ peak around 9-10 eV and decrease at higher energies. Average photodesorption yields of intact water at 15 K are 5 $\times$ 10$^{-4}$ molecule/photon for H$_2$O and 5 $\times$ 10$^{-5}$ molecule/photon for D$_2$O over the 7-13.5 eV range. The strong isotopic effect can be explained by a differential chemical recombination between OH (OD) and H (D) photofragments originating from lower kinetic energy available for the OH photofragments upon direct water photodissociation and/or possibly by an electronic relaxation process. It is expected to contribute to water fractionation during the building-up of the ice grain mantles in molecular clouds and to favor OH-poor chemical environment in comet-formation regions of protoplanetary disks. The yields of all the detected species except OH (OD) are enhanced above (70 $\pm$10) K, suggesting an ice restructuration at this temperature., Comment: Submitted to A&A. In revision

The Sentinel-5 Precursor (S5P) mission with the TROPOspheric Monitoring Instrument (TROPOMI) onboard has been measuring solar radiation backscattered by the Earth's atmosphere and its surface since its launch on 13 October 2017. Methane (CH4) and carbon monoxide (CO) data with a spatial resolution (initially 7 x 7 km2, upgraded to 5.5 x 7 km2 on 6th of August 2019) have been retrieved from shortwave infrared (SWIR) and near-infrared (NIR) measurements since the end of November 2017 and made available to the experts for early validation and quality checks before the official product release. In this paper, we present for the first time the S5P CH4 and CO validation results (covering a period from November 2017 to September 2020) using global Total Carbon Column Observing Network (TCCON) and Infrared Working Group of the Network for the Detection of Atmospheric Composition Change (NDACC-IRWG) network data, accounting for a priori alignment and smoothing uncertainties in the validation, and testing the sensitivity of validation results towards the application of advanced co-location criteria.We found that the required bias (systematic error) of 1.5 % and random error of 1 % for the S5P standard and bias-corrected methane data are met for measurements over land surfaces with pixels having quality assurance (QA) value > 0.5. The systematic difference between the S5P standard XCH4 and TCCON data is on average −0.69 ± 0.73 %. The systematic difference changes to a value of −0.25 ± 0.57 % for the S5P bias-corrected XCH4 data. We found a correlation of above 0.6 for most stations, which is mostly dominated by the seasonal cycle. The contributions of smoothing uncertainty at the individual stations are estimated and found to be dependent on the location. The highest contribution of the smoothing uncertainty is observed for mid-latitude TCCON stations and high latitude stations for NDACC. A seasonal dependency of the relative bias is seen. We observe a high bias during the springtime measurements at high SZA and a decreasing bias with increasing SZA for the rest of the year.We found that the required bias (systematic error) of 15 % and random error of < 10 % for the S5P carbon monoxide data are met in general for measurements over all surfaces with pixels having quality assurance value of > 0.5. There are a few stations where this is not the case, mostly due to co-location mismatches and the limited availability of co-located data. We compared the S5P XCO data with respect to standard TCCON XCO and unscaled TCCON XCO (without application of the empirical scaling factor) data sets. The systematic difference between the S5P XCO and the TCCON data is on average 9.14 ± 3.33 % (standard TCCON XCO data) and 2.36 ± 3.22 % (unscaled TCCON XCO data). We found that the systematic difference between the S5P CO column and NDACC CO column data (excluding two stations that were obvious outliers) is on average 6.44 ± 3.79 %. We found a correlation of above 0.9 for most TCCON and NDACC stations indicating that the temporal variations in CO column captured by the ground-based instruments are reproduced very similarly by the S5P CO column. The contribution of smoothing uncertainty at the individual stations is estimated and found to be significant. They are found to be dependent on the location with large changes seen for stations located in the Southern Hemisphere as compared to the Northern Hemisphere and at highly polluted stations. A cone co-location criterion, which gives a better match between the ground-based instrument's line-of-sight and satellite pixels, seems to give better results for high latitude stations and stations located close to emission sources. The validation results for the clear-sky and cloud cases of S5P pixels are comparable to the validation results including all pixels with quality assurance value of > 0.5. We observe that the relative bias increases with increasing SZA. We estimated this increase is about 10 % over the complete range of measurement SZAs.The study shows the high quality of S5P CH4 and CO data by validating the products against reference global TCCON and NDACC stations covering a wide range of latitudinal bands, atmospheric conditions, and surface conditions.

Although optical components in Fourier transform infrared (FTIR) spectrometers are preferably wedged, in practice, infrared spectra typically suffer from the effects of optical resonances (“channeling”) affecting the retrieval of weakly absorbing gases. This study investigates the level of channeling of each FTIR spectrometer within the Network for the Detection of Atmospheric Composition Change (NDACC). Dedicated spectra were recorded by more than twenty NDACC FTIR spectrometers using a laboratory mid-infrared source and two detectors. In the InSb detector domain (1900–5000 cm−1), we find that the amplitude of the most pronounced channeling frequency amounts to 0.1 to 2.0 ‰ of the spectral background level, with a mean of (0.68 ± 0.48) ‰ and a median of 0.60 ‰. In the HgCdTe detector domain (700–1300 cm−1), we find even stronger effects, with the largest amplitude ranging from 0.3 to 21 ‰ with a mean of (2.45 ± 4.50) ‰ and a median of 1.2 ‰. For both detectors, the leading channeling frequencies are 0.9 and 0.11 or 0.23 cm−1 in most spectrometers. These observed spectral frequencies correspond to the optical thickness of the air gap in between the beam splitter and compensator plate (0.9 cm−1) and the beam splitter substrate itself (0.11 and 0.23 cm−1). Since the air gap is a significant source of channeling and the corresponding amplitude differs strongly between spectrometers, we propose new beam splitters with the wedge of the air gap increased to at least 0.8°. We tested the insertion of spacers in a beam splitter’s air gap to demonstrate that increasing the wedge of the air gap decreases the 0.9 cm−1 channeling amplitude significantly. This study shows the potential for reducing channeling in the FTIR spectrometers operated by the NDACC, thereby increasing the quality of recorded spectra across the network.

Measurements of vertical concentration profiles of greenhouse gases (GHGs) is extremely important for our understanding of regional air quality and global climate change trends. In this context, laser heterodyne radiometer (LHR) technique has been developed [1-5] for ground-based remote measurements of GHGs in the atmospheric column.Solar radiation undergoing absorption by multi-species in the atmosphere is coupled into a LHR instrument where the sunlight is mixed with a local oscillator (LO), being usually a tunable laser source, in a fast photodetector. Beating note at radio frequency (RF) resulted from this photomixing contains absorption information of the LO-targeted molecules. Scanning the LO frequency across the target molecular absorption lines allows one to extract the corresponding absorption features from the total absorption of the solar radiation by all molecules in the atmospheric column. Near-IR (~1.5 µm) and mid-IR (~8 µm) [6] LHRs have been recently developed in the present work. Field campaigns have been performed on the roof of the platform of IRENE in Dunkerque (51.05°N/2.34°E).The developed LHR instruments as well as the preliminary results of their applications to the measurements of CH4, N2O, CO2 (including 13CO2/12CO2), H2O vapor (and its isotopologue HDO) in the atmospheric column will be presented and discussed.Acknowledgments The authors thank the financial supports from the LABEX CaPPA project (ANR-10-LABX005), the MABCaM (ANR-16-CE04-0009) and the MULTIPAS (ANR-16-CE04-0012) contracts, as well as the CPER CLIMIBIO program. S. F. thanks the program Labex CaPPA and the "Pôle Métropolitain de la Côte d’Opale" (PMCO) for the PhD fellowship support.References [1] R. T. Menzies, and R. K. Seals, Science 197 (1977) 1275-1277[2] D. Weidmann, T. Tsai, N. A. Macleod, and G. Wysocki, Opt. Lett. 36 (2011) 1951-1953[3] E. L. Wilson, M. L. McLinden, and J. H. Miller, Appl. Phys. B 114 (2014) 385-393[4] A. Rodin, A. Klimchuk, A. Nadezhdinskiy, D. Churbanov, and M. Spiridonov, Opt. Express 22 (2014) 13825-13834[5] J. Wang, G. Wang, T. Tan, G. Zhu, C. Sun, Z. CAO, W. Chen, and X. Gao, Opt. Express 27 (2019) 9600-9619[6] F. Shen, P. Jeseck, Y. Te, T. Tan, X. Gao, E. Fertein, and W. Chen, Geophys. Res. Abstracts, 20 (2018) EGU2018-79

We characterize the magnitude of seasonally and spatially varying biases in the National Aeronautics and Space Administration (NASA) Orbiting Carbon Observatory-2 (OCO-2) Version 8 (v8) and the Atmospheric CO2 Observations from Space (ACOS) Greenhouse Gas Observing SATellite (GOSAT) version 7.3 (v7.3) satellite CO2 retrievals by comparisons to measurements collected by the Total Carbon Column Observing Network (TCCON), Atmospheric Tomography (ATom) experiment, and National Oceanic and Atmospheric Administration (NOAA) Earth System Research Laboratory (ESRL) and U. S. Department of Energy (DOE) aircraft, and surface stations. Although the ACOS-GOSAT estimates of the column averaged carbon dioxide (CO2) dry air mole fraction (XCO2) have larger random errors than the OCO-2 XCO2 estimates, and the space-based estimates over land have larger random errors than those over ocean, the systematic errors are similar across both satellites and surface types, 0.6 ± 0.1 ppm. We find similar estimates of systematic error whether dynamic versus geometric coincidences or ESRL/DOE aircraft versus TCCON are used for validation (over land), once validation and co-location errors are accounted for. We also find that areas with sparse throughput of good quality data (due to quality flags and preprocessor selection) over land have ~double the error of regions of high-throughput of good quality data. We characterize both raw and bias-corrected results, finding that bias correction improves systematic errors by a factor of 2 for land observations and improves errors by ~ 0.2 ppm for ocean. We validate the lowermost tropospheric (LMT) product for OCO-2 and ACOS-GOSAT by comparison to aircraft and surface sites, finding systematic errors of ~ 1.1 ppm, while having 2–3 times the variability of XCO2. We characterize the time and distance scales of correlations for OCO-2 XCO2 errors, and find error correlations on scales of 0.3 degrees, 5–10 degrees, and 60 days. We find comparable scale lengths for the bias correction term. Assimilation of the OCO-2 bias correction term is used to estimate flux errors resulting from OCO-2 seasonal biases, finding annual flux errors on the order of 0.3 and 0.4 PgC/yr for Transcom-3 ocean and land regions, respectively.

Observations of carbon monoxide (CO) from the Measurements Of Pollution In The Troposphere (MOPITT) instrument onboard the Terra spacecraft were expected to have an accuracy of 10 % prior to launch in 1999. Here we evaluate MOPITT version 7 joint TIR-NIR (V7J) accuracy and precision, and suggest ways to further improve the accuracy of the observations. We take five steps involving filtering or bias corrections to reduce scatter and bias in the data relative to other MOPITT soundings, and ground based measurements. 1) We apply a preliminary filtering scheme in which measurements over snow and ice are removed. 2) We find a systematic pairwise bias among the four MOPITT along-track detectors (pixels) on the order of 3–4 ppb with a small temporal trend, which we remove on a global scale using a temporally trended bias correction. 3) Using a small region approximation (SRA) a new filtering scheme is developed and applied based on additional quality indicators such as signal-to-noise. After applying these new filters, the root mean squared error computed using the local median from the SRA over 16 years of global observations decreases from 3.84 ppb to 2.55 ppb. 4) We also use the SRA to find variability in MOPITT retrieval anomalies that relates to retrieval parameters. We apply a bias correction to one parameter from this analysis. 5) After applying the previous bias corrections and filtering, we compare the MOPITT results with the GGG2014 ground-based Total Carbon Column Observing Network (TCCON) observations to obtain an overall global bias correction. These comparisons show that MOPITT V7J is biased high by about 6–8 %, which is similar to past studies using independent validation datasets on V6J. When using TCCON spectrometric column retrievals without the standard airmass correction or scaling to aircraft (WMO scale), the ground and satellite based observations overall agree to better than 0.5 %. GEOS-Chem data assimilations are used to estimate the influence of filtering and scaling to TCCON on global CO, and tend to pull concentrations away from the prior, and closer to the truth. We conclude with suggestions for further improving the MOPITT data products.

Non-thermal desorption from icy grains containing H$_2$CO has been invoked to explain the observed H$_2$CO gas phase abundances in ProtoPlanetary Disks (PPDs) and Photon Dominated Regions (PDRs). Photodesorption is thought to play a key role, however no absolute measurement of the photodesorption from H$_2$CO ices were performed up to now, so that a default value is used in the current astrophysical models. As photodesorption yields differ from one molecule to the other, it is crucial to experimentally investigate photodesorption from H$_2$CO ices. We measured absolute wavelength-resolved photodesorption yields from pure H$_2$CO ices, H$_2$CO on top of a CO ice (H$_2$CO/CO), and H$_2$CO mixed with CO ice (H$_2$CO:CO) irradiated in the Vacuum UltraViolet (VUV) range (7-13.6~eV). Photodesorption from a pure H$_2$CO ice releases H$_2$CO in the gas phase, but also fragments, such as CO and H$_2$. Energy-resolved photodesorption spectra, coupled with InfraRed (IR) and Temperature Programmed Desorption (TPD) diagnostics, showed the important role played by photodissociation and allowed to discuss photodesorption mechanisms. For the release of H$_2$CO in the gas phase, they include Desorption Induced by Electronic Transitions (DIET), indirect DIET through CO-induced desorption of H$_2$CO and photochemical desorption. We found that H$_2$CO photodesorbs with an average efficiency of $\sim 4-10 \times 10^{-4}$ molecule/photon, in various astrophysical environments. H$_2$CO and CO photodesorption yields and photodesorption mechanisms, involving photofragmentation of H$_2$CO, can be implemented in astrochemical codes. The effects of photodesorption on gas/solid abundances of H$_2$CO and all linked species from CO to Complex Organic Molecules (COMs), and on the H$_2$CO snowline location, are now on the verge of being unravelled., ACS Earth and Space Chemistry; Complex Organic Molecules (COMs) in Star-Forming Regions special issue

The infrared gas-phase absorption spectrum of methane was used to determine its Clapeyron solid–gas equilibrium curve in the 40–77 K temperature range. For comparative purposes and to obtain more reliable results, two different optical experimental setups were used. At higher temperatures (53–77 K), a single pass cryogenically cooled cell was coupled to a standard low-resolution Fourier transform infrared spectrometer. The second system was a state-of-the-art vertical-external-cavity surface-emitting laser tunable source operating at around 2.3 μm, combined with a 7 m path Herriott cell, to record methane absorption features down to 40 K. From the measurements, the vapor pressure curve ln(p/Pa) = −(1191.92 ± 8.92)/(T/K) + (22.49 ± 0.16) was derived in the range 40–77 K. This corresponds to a value of 9910 ± 75 J mol–1 for the sublimation enthalpy. The relation was validated down to 40 K, increasing our knowledge of the saturation pressure by 2 orders of magnitude. Data were compared with available pressur...

Providing timely information on urban Greenhouse-Gas (GHG) emissions and their trends to stakeholders relies on reliable measurements of atmospheric concentrations and the understanding of how local emissions and atmospheric transport influence these observations. Portable Fourier Transform Infra-Red (FTIR) spectrometers were deployed at 5 stations in the Paris metropolitan area to provide column-averaged concentrations of CO2 (XCO2) during a field campaign in spring of 2015. Here, we describe and analyze the variations of XCO2 observed at different sites and how they changed over time. We find that observations upwind and downwind of the city centre differ significantly in their XCO2 concentrations, while the overall variability of the daily cycle is similar, i.e., increasing during night-time with a strong decrease (typically 2–3 ppm) during the afternoon. An atmospheric transport model framework (CHIMERE-CAMS) was used to simulate XCO2 and predict the same behaviour seen in the observations, which supports key findings, e.g. that even in a densely populated region like Paris (over 12 Million people), biospheric uptake of CO2 can be of major influence on daily XCO2 variations. Despite a general offset between modelled and observed XCO2, the model correctly predicts the impact of the meteorological parameters (e.g. wind direction and speed) on the concentration gradients between different stations. Looking at the local gradients of XCO2 for upwind and downwind station pairs, which is less sensitive to changes in XCO2 regional background conditions, we find the model-data agreement significantly better. Our modelling framework indicates that the local XCO2 gradient between the stations is dominated by the fossil fuel CO2 signal of the Paris metropolitan area. This highlights the usefulness of XCO2 observations to help optimise future urban GHG emission estimates.

Water is the main constituent of interstellar ices, and it plays a key role in the evolution of many regions of the interstellar medium, from molecular clouds to planet-forming disks1. In cold regions of the interstellar medium, water is expected to be completely frozen out onto the dust grains. Nonetheless, observations indicate the presence of cold water vapour, implying that non-thermal desorption mechanisms are at play. Photodesorption by ultraviolet photons has been proposed to explain these observations2,3, with the support of extensive experimental and theoretical work on ice analogues4–6. In contrast, photodesorption by X-rays, another viable mechanism, has been little studied. The potential of this process to desorb key molecules such as water, intact rather than fragmented or ionized, remains unexplored. We experimentally investigated X-ray photodesorption from water ice, monitoring all desorbing species. We found that desorption of neutral water is efficient, while ion desorption is minor. We derived yields that can be implemented in astrochemical models. These results open up the possibility of taking into account the X-ray photodesorption process in the modelling of protoplanetary disks or X-ray-dominated regions. The X-ray-induced photodesorption of water from astrophysical ices, intact, has been little studied. However, it could be a key process in producing the cold water vapour that is seen in these regions. Here, the yield of such a mechanism is experimentally quantified.

An mid-infrared laser heterodyne radiometer was been developed for ground-based remote measurements of greenhouse gases (GHGs) in the atmospheric column.

An mid-infrared laser heterodyne radiometer was been developed for ground-based remote measurements of greenhouse gases (GHGs) in the atmospheric column.

Context. Methane is among the main components of the ice mantles of interstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims. This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules are monitored and quantified. Methods. Tunable monochromatic vacuum ultraviolet light (VUV) light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7–13.6 eV (177–91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry, and absolute photodesorption yields of intact CH4 are deduced. Results. CH4 photodesorbs for photon energies higher than ~9.1 eV (~136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions. The photodesorption of CH4 from pure ice in various interstellar environments is around 2.0 ± 1.0 × 10-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles.

The study and quantification of UV photon-induced desorption of frozen molecules furthers our understanding of the chemical evolution of cold interstellar regions. Nitric oxide (NO) is an important intermediate species in both gas-phase and solid-phase chemical networks. In this work, we present quantitative measurements of the photodesorption of a pure NO ice.We used the tunable monochromatic synchrotron light of the DESIRS beamline of the SOLEIL facility near Paris to irradiate NO ices in the 6 - 13.6 eV range and measured desorption by quadrupole mass spectrometry.We find that NO photodesorption is very efficient, its yield being around 1e-2 molecule per incident photon for UV fields relevant to the diffuse and dense interstellar medium. We discuss the extrapolation of our results to an astrophysical context and we compare photodesorption of NO to previously studied molecules., Comment: A&A, Accepted

Nowadays, more than 50% of the global population leave in urban centers which activities generate large anthropogenic emissions of CO2 (more than 70% of fossil fuel CO2 comes from urbanized/industrialized areas) and reactive gases that endanger our climate, the health of human beings and surrounding ecosystems. The worst situations are encountered during urban pollution events that usually form under anticyclonic conditions. Analyzing the contribution of the local and regional sources of urban CO2 and co-emitted species vs the remote ones, as well as the nature of these sources and the dynamical processes that lead to the building of such events can provide interesting knowledge for helping urban policy makers to better identify the role of anthropogenic/biogenic sources on the urban air composition and to take proper decisions in matter of CO2 and pollutants sources mitigation. With 12 million of people, Paris (France) is the second megacity in Europe. In 2016, two pollution events occured in the Paris region during which the instrumental platform OCAPI (http://observations.ipsl.fr/composition-atmospherique-en-idf.html) from IPSL (Institut Pierre Simon Laplace) was mobilized in collaboration with air quality governing actors (AIRPARIF, INERIS) to collect a bunch of observations. Five sites located in the urban, peri-urban and rural areas of Paris were equiped with in-situ analyzers (CO2, CO, black carbon, 13CO2, COS) ; Fourier transform spectrometers for column measurements (XCO2, XCO, XCOS), particle filters (for aerosols size and content analysis) ; air samples (levoglucosan, 14CO2, VOCs) ; and Lidar profilers (boundary layer height ; wind profiles). These data, combined with a backtrajectories analysis, give information about the dynamical processes that lead to the formation of the pollution events and on the contribution of local, regional and remote sources. The analysis of the correlations between the trace species and of the isotopic content of carbon in CO2 provides further clues on the nature of the anthropogenic and biogenic sources involved in the urban pollution events. Especially, the role of agricultural spreading through the observation of ammonium nitrate particles and the contribution of biomass burning through levoglucosan and black carbon measurements will be discussed.

The SPIRALE and SWIR balloon-borne instruments were launched in the Arctic polar region (near Kiruna, Sweden, 67.9° N–21.1° E) during summer on 7 and 24 August 2009 and on 14 August 2009, respectively. The SPIRALE instrument performed in situ measurements of several trace gases including CO and O3 at altitudes between 9 and 34 km, with very high vertical resolution (∼ 5 m). The SWIR-balloon instrument measured total and partial column of several species including CO. The CO stratospheric profile from SPIRALE for 7 August 2009 shows some specific structures with large concentrations in the low levels (potential temperatures between 320 and 380 K, i.e. 10–14 km height). These structures are not present in the CO vertical profile of SPIRALE for 24 August 2009, for which the volume mixing ratios are typical from polar latitudes (∼ 30 ppb). CO total columns retrieved from the IASI-MetOp satellite sounder for the three dates of flights are used to understand this CO variability. SPIRALE and SWIR CO partial columns between 9 and 34 km are compared, allowing us to confirm that the enhancement of CO is localised in the stratosphere. The measurements are also investigated in terms of CO:O3 correlations and using several modelling approaches (trajectory calculations, potential vorticity fields, results of chemistry transport model) in order to characterize the origin of the air masses sampled. The emission sources are qualified in terms of source type (fires, urban pollution) using NH3 and CO measurements from IASI-MetOp and fires detection from MODIS on board the TERRA/AQUA satellite. The results give strong evidence that the unusual abundance of CO on 7 August is due to surface pollution plumes from East Asia and North America transporting to the upper troposphere and then entering the lower stratosphere by isentropic advection. This study strengthens evidence that the composition of low polar stratosphere in summer may be affected by anthropogenic surface emissions through long-range transport.

NASA's Orbiting Carbon Observatory-2 (OCO-2) has been measuring carbon dioxide column-averaged dry air mole fractions, XCO2, in the Earth’s atmosphere for almost two years. In this paper, we describe the comparisons between the OCO-2 version 7Br retrievals and XCO2 estimates from OCO-2's primary ground-based validation network: the Total Carbon Column Observing Network (TCCON). The OCO-2 XCO2 retrievals, after bias correction, agree well globally with the TCCON for nadir, glint, and target observations, with median differences less than 0.5 ppm and RMS differences typically below 1.5 ppm. Target observations over TCCON stations correlate best with the TCCON data (R2 = 0.83) on a global scale. At local scales, the target comparisons reveal residual biases likely related to surface properties and aerosol scattering. It is thus crucial to continue measurement comparisons with TCCON to monitor and evaluate the OCO-2 XCO2 data quality throughout its mission.

Carbon monoxide (CO) is an atmospheric key species due to its toxicity and its impact on the atmospheric oxidizing capacity, both factors affecting air quality. The paper studies the altitude dependent seasonal variability of CO at the three different sites Paris, Jungfraujoch and Wollongong, with an emphasis on establishing a link between the CO vertical distribution and the nature of CO emission sources. The CO seasonal variability obtained from the total columns and from the free tropospheric partial columns shows a maximum around March-April and a minimum around September-October in the Northern Hemisphere (Paris and Jungfraujoch). In the Southern Hemisphere (Wollongong) this seasonal variability is shifted by about 6 months. Satellite observations by IASI-MetOp and MOPITT instruments confirm this seasonality. Ground-based FTIR is demonstrated to provide useful complementary information due to good sensitivity in the boundary layer. In situ surface measurements of CO volume mixing ratios in Paris and at Jungfraujoch reveal a time-lag of the near surface seasonal variability of about 2 months with respect to the total column variability at the same sites. The chemical transport model GEOS-Chem is employed to interpret our observations. GEOS-Chem sensitivity runs allow identifying the emission sources influencing the seasonal cycle of CO. In Paris and on top of Jungfraujoch, the surface seasonality is mainly driven by anthropogenic emissions, while the total column seasonality is also controlled by air masses transported from distant sources. In the case of Wollongong, where the CO seasonality is mainly affected by biomass burning, no time shift is observed between surface and above the boundary layer.

A spectroscopic study of methane spectra in the range around 6764 cm −1 was performed at different temperatures (from 55 to 200 K). The recorded spectra were used to increase the precision of transitions lower states energy determination and to retrieve the self-collisional broadening parameter. Both the newly obtained results and the quality of the experimental data were used to evaluate our system in the perspective of nuclear spin conversion measurements.

Analysis of the temperature dependence of the ratio of the intensity of two assigned and unassigned lines enables the determination of the most probable energy of the lower state of the unassigned transition. Such a new procedure has been applied to transitions of ammonia in the range 6626.0–6668.5 cm−1 between 122 K and 300 K. This represents a first step in the considerable task of the assignment of the complete 1.5 μ m infrared spectral range.

Context. Over 20 of the ~150 different species detected in the interstellar and circumstellar media have also been identified in icy environments. For most of the species observed so far in the interstellar medium (ISM), the most abundant isomer of a given generic chemical formula is the most stable one (minimum energy principle – MEP) with few exceptions such as, for example, CH3COOH/HCOOCH3 and CH3CH2OH/CH3OCH3, whose formation is thought to occur on the icy mantles of interstellar grains. Aims. We investigate whether differences found in the compositions of molecular ices and the surrounding gas phase could originate from differences between the adsorption of one isomer from that of another at the ice surface. Methods. We performed a coherent and concerted theoretical/experimental study of the adsorption energies of the four molecules mentioned above, i.e. acetic acid (AA)/methyl formate (MF) and ethanol (EtOH)/dimethyl ether (DME) on the surface of water ice at low temperature. The question was first addressed theoretically at LCT using solid state periodic density functional theory (DFT) to represent the organized solid support. The experimental determination of the ice/molecule interaction energies was then carried out independently by two teams at LPMAA and LERMA/LAMAp using temperature programmed desorption (TPD) under an ultra-high vacuum (UHV) between 70 and 160 K. Results. For each pair of isomers, theory and experiments both agree that the most stable isomer (AA or EtOH) interacts more efficiently with the water ice than the higher energy isomer (MF or DME). This differential adsorption can be clearly seen in the different desorption temperatures of the isomers. It is not related to their intrinsic stability but instead to both AA and EtOH producing more and stronger hydrogen bonds with the ice surface. Conclusions. We show that hydrogen bonding may play an important role in the release of organic species from grains and propose that, depending on the environment, differential adsorption should not be rejected as a possible way of interpreting MEP exceptions.

International audience; Carbonyl sulfide (OCS) is an important precursor of sulfate aerosols and consequently a key species in stratospheric ozone depletion. SPIRALE and SWIR balloon-borne instruments have flown in the tropical region and in the Arctic polar region, and ground-based measurements have been performed by QualAir FTS instrument in Paris. Partial and total columns and vertical profiles have been obtained to study the OCS variability with altitude, latitude and season. The annual total column variation in Paris reveals a seasonal variation with a maximum in April-June and a minimum in November-January. Total column measurements above Paris and from SWIR balloon-borne instrument are compared with several MkIV measurements, several NDACC stations, aircraft, ship and balloon measurements to highlight the OCS total column decrease from tropical to polar latitudes. OCS high resolution in situ vertical profiles have been measured for the first time in the altitude range between 14 and 30 km at tropical and polar latitudes. OCS profiles are compared with ACE satellite measurements and show good agreement. Using OCS:N2O correlation from SPIRALE, OCS stratospheric lifetime has been accurately determined. We find a stratospheric lifetime of 70±20 years at polar latitude and 58±14 years at tropical latitude leading to a global stratospheric sink of 54±14 Gg S yr-1.

Resume La spectroscopie infrarouge est un outil puissant pour mesurer precisement les concentrations d'especes a l'etat de trace dans l'atmosphere par l'utilisation des signatures spectrales, caracteristiques des differentes especes moleculaires, qui sont associees aux bandes de vibration–rotation dans l'infrarouge moyen ou proche. Differentes methodes basees sur la spectroscopie quantitative permettent de realiser des mesures tropospheriques ou stratospheriques : absorption a long parcours in situ, absorption/emission atmospherique par spectrometrie de Fourier avec des instruments a haute resolution spectrale installes au sol ou embarques a bord d'avion, sous ballon ou sur satellite.

Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N2 and O2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N2 and O2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. N2 photodesorption mainly occurs through excitation of the b^1Pi_u state and subsequent desorption of surface molecules. The observed vibronic structure in the N2 photodesorption spectrum, together with the absence of N3 formation, supports that the photodesorption mechanism of N2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O2 photodesorption in the 7 - 13.6 eV range occurs through dissociation and presents no vibrational structure. Photodesorption rates of N2 and O2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10E-3 and 10E-2 photodesorbed molecules per incoming photon., Comment: 7 pages, 5 figures, published in A&A

UV ice photodesorption is an important non-thermal desorption pathway in many interstellar environments that has been invoked to explain observations of cold molecules in disks, clouds and cloud cores. Systematic laboratory studies of the photodesorption rates, between 7 and 14 eV, from CO:N2 binary ices, have been performed at the DESIRS vacuum UV beamline of the synchrotron facility SOLEIL. The photodesorption spectral analysis demonstrates that the photodesorption process is indirect, i.e. the desorption is induced by a photon absorption in sub-surface molecular layers, while only surface molecules are actually desorbing. The photodesorption spectra of CO and N2 in binary ices therefore depend on the absorption spectra of the dominant species in the subsurface ice layer, which implies that the photodesorption efficiency and energy dependence are dramatically different for mixed and layered ices compared to pure ices. In particular, a thin (1-2 ML) N2 ice layer on top of CO will effectively quench CO photodesorption, while enhancing N2 photodesorption by a factors of a few (compared to the pure ices) when the ice is exposed to a typical dark cloud UV field, which may help to explain the different distributions of CO and N2H+ in molecular cloud cores. This indirect photodesorption mechanism may also explain observations of small amounts of complex organics in cold interstellar environments., 21 pages 5 figures