Search

For the past 17 years, the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) instrument on the Canadian SCISAT satellite has been measuring profiles of atmospheric ozone. The latest operational versions of the level 2 ozone data are versions 3.6 and 4.1. This study characterizes how both products compare with correlative data from other limb-sounding satellite instruments, namely MAESTRO, MLS, OSIRIS, SABER, and SMR. In general, v3.6, with respect to the other instruments, exhibits a smaller bias (which is on the order of ∼ 3 %) in the middle stratosphere than v4.1 (∼ 2 %–9 %); however, the bias exhibited in the v4.1 data tends to be more stable, i.e. not changing significantly over time in any altitude region. In the lower stratosphere, v3.6 has a positive bias of about 3 %–5 % that is stable to within ±1 % per decade, and v4.1 has a bias on the order of −1 % to +5 % and is also stable to within ±1 % per decade. In the middle stratosphere, v3.6 has a positive bias of ∼ 3 % with a significant negative drift on the order of 0.5 %–2.5 % per decade, and v4.1 has a positive bias of 2 %–9 % that is stable to within ±0.5 % per decade. In the upper stratosphere, v3.6 has a positive bias that increases with altitude up to ∼ 16 % and a significant negative drift on the order of 2 %–3 % per decade, and v4.1 has a positive bias that increases with altitude up to ∼ 15 % and is stable to within ±1 % per decade. Estimates indicate that both versions 3.6 and 4.1 have precision values on the order of 0.1–0.2 ppmv below 20 km and above 45 km (∼ 5 %–10 %, depending on altitude). Between 20 and 45 km, the estimated v3.6 precision of ∼ 4 %–6 % is better than the estimated v4.1 precision of ∼ 6 %–10 %.

This study presents upper troposphere–lower stratosphere (UTLS) water vapour and ozone climatologies generated from 14 years (June 2004 to May 2018) of measurements made by three Canadian limb-viewing satellite instruments: the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (MAESTRO), and the Optical Spectrograph and InfraRed Imaging System (OSIRIS; ozone only). This selection of instruments was chosen to explore the capability of these Canadian instruments in representing the UTLS and to enable analysis of the impact of different measurement sampling patterns. The water vapour and ozone climatologies have been constructed using tropopause-relative potential temperature and equivalent-latitude coordinates in an effort to best represent the distribution of these two gases in the UTLS, which is characterized by a high degree of dynamic and geophysical variability. Zonal-mean multiyear-mean climatologies are provided with 5∘ equivalent latitude and 10 K potential temperature spacing and have been constructed on a monthly, seasonal (3-month), and yearly basis. These climatologies are examined in-depth for two 3-month periods, December–January–February and June–July–August, and are compared to reference climatologies constructed from the Canadian Middle Atmosphere Model 39-year specified dynamics (CMAM39-SD) run, subsampled to the times and locations of the satellite measurements, in order to evaluate the consistency of water vapour and ozone between the datasets. Specifically, this method of using a subsampled model addresses the impact of each instrument's measuring pattern and allows for the quantification of the influence of different measurement patterns on multiyear climatologies. This in turn permits a more consistent evaluation of the distributions of these two gas species, as assessed through the differences between the model and measurement climatologies. For water vapour, the average absolute relative difference between CMAM39-SD and ACE-FTS differed between the two versions of ACE-FTS by less than 8 %, while the MAESTRO climatologies were found to differ by 15 %–41 % from ACE-FTS, depending on the version of ACE-FTS and the season. When considering the ozone climatologies, those constructed from the two ACE-FTS versions agreed to within 2 % overall, and the OSIRIS ozone climatologies agreed with these to within 10 %. The MAESTRO ozone climatologies differ from those from ACE-FTS and OSIRIS by 30 %–35 % and 25 %, respectively, albeit with regions of better agreement within the UTLS. These findings indicate that this set of Canadian limb sounders yields generally similar water vapour and ozone distributions in the UTLS, with some exceptions for MAESTRO depending on the season and gas species.

In order to validate satellite measurements of atmospheric composition, it is necessary to understand the range of random and systematic uncertainties inherent in the measurements. On occasions where measurements from two different satellite instruments do not agree within those estimated uncertainties, a common explanation is that the difference can be assigned to geophysical variability, i.e., differences due to sampling the atmosphere at different times and locations. However, the expected geophysical variability is often left ambiguous and rarely quantified. This paper describes a case study where the geophysical variability of O3 between two satellite instruments – ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) and OSIRIS (Optical Spectrograph and InfraRed Imaging System) – is estimated using simulations from climate models. This is done by sampling the models CMAM (Canadian Middle Atmosphere Model), EMAC (ECHAM/MESSy Atmospheric Chemistry), and WACCM (Whole Atmosphere Community Climate Model) throughout the upper troposphere and stratosphere at times and geolocations of coincident ACE-FTS and OSIRIS measurements. Ensemble mean values show that in the lower stratosphere, O3 geophysical variability tends to be independent of the chosen time coincidence criterion, up to within 12 h; and conversely, in the upper stratosphere geophysical variation tends to be independent of the chosen distance criterion, up to within 2000 km. It was also found that in the lower stratosphere, at altitudes where there is the greatest difference between air composition inside and outside the polar vortex, the geophysical variability in the southern polar region can be double of that in the northern polar region. This study shows that the ensemble mean estimates of geophysical variation can be used when comparing data from two satellite instruments to optimize the coincidence criteria, allowing for the use of more coincident profiles while providing an estimate of the geophysical variation within the comparison results.

Phosgene in the atmosphere is produced via the degradation of carbon tetrachloride, methyl chloroform, and a number of chlorine‐containing very short lived substances (VSLS). These VSLS are not regulated by the Montreal Protocol even though they contribute to stratospheric ozone depletion. While observations of VSLS can quantify direct stratospheric source gas injection, observations of phosgene in the upper troposphere/lower stratosphere can be used as a marker of product gas injection of chlorine‐containing VSLS. In this work we report upper troposphere/lower stratosphere measurements of phosgene made by the ACE‐FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) instrument and compare with results from the TOMCAT/SLIMCAT three‐dimensional chemical transport model to constrain phosgene trends over the 2004–2016 period. The 13‐year ACE‐FTS time series provides the first observational evidence for an increase in chlorine product gas injection. In 2016, VSLS accounted for 27% of modeled stratospheric phosgene, up from 20% in the mid‐2000s.

Since 2004, the Atmospheric Chemistry Experiment – Fourier Transform Spectrometer (ACE-FTS) instrument has been measuring concentrations of chlorofluorocarbons (CFCs) in the stratosphere and upper troposphere and is currently the only satellite instrument that measures vertically resolved profiles of CFC‑11. Since CFCs are major ozone depleting substances, monitoring their atmospheric abundances is critical for understanding ozone layer recovery. Recent studies based solely on surface-level measurements have shown strong evidence for new CFC‑11 production, leading to an increase in CFC‑11 emissions over the past decade. In this study, the TOMCAT/SLIMCAT 3-D chemical transport model is used in order to bridge the altitude/geolocation gap between ACE-FTS measurements in the UTLS and surface level measurements. Trends in two different time periods over the ACE-FTS mission, 2004-2012 and 2013-2018, are examined to determine if the recent change in surface level CFC-11 trends is influencing UTLS concentrations. The ACE-FTS measurements show that, below ~10 km, the rate of decrease of global CFC-11 concentrations was slower during 2013-2018 (-1.2 pptv/year) than during 2004-2012 (‑2.0 pptv/year). Similar trends are observed in the model data for the same spatial/temporal regions.

This paper outlines the major updates of the line-shape parameters that were performed for the nitrous oxide (N 2 O) and carbon monoxide (CO) molecules listed in the HITRAN2020 database. We reviewed the collected measurements for the air- and self-broadened N 2 O and CO spectra to determine proper values for the spectroscopic parameters. Careful comparisons of broadening parameters using the Voigt and speed-dependent Voigt line-shape profiles were performed among various published results for both N 2 O and CO. Selected data allowed for developing semi-empirical models, which were used to extrapolate/interpolate existing data to update broadening parameters of all the lines of these molecules in the HITRAN database. In addition to the line broadening parameters (and their temperature dependences), the pressure shift values were revised for N 2 O and CO broadened by air and self for all the bands. The air and self speed-dependence of the broadening parameter for these two molecules were added for every transition as well. Furthermore, we determined the first-order line-mixing parameters using the Exponential Power Gap (EPG) scaling law. These new parameters are now available at HITRAN o n l i n e .

Atmospheric emissions of carbon tetrachloride (CCl4) are regulated by the Montreal Protocol due to its role as a strong ozone-depleting substance. The molecule has been the subject of recent increased interest as a consequence of the so-called mystery of CCl4, the discrepancy between atmospheric observations and reported production and consumption. Surface measurements of CCl4 atmospheric concentrations have declined at a rate almost 3 times lower than its lifetime-limited rate, suggesting persistent atmospheric emissions despite the ban. In this paper, we study CCl4 vertical and zonal distributions in the upper troposphere and lower stratosphere (including the photolytic loss region, 70–20 hPa), its trend, and its stratospheric lifetime using measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), which operated onboard the ENVISAT satellite from 2002 to 2012. Specifically, we use the MIPAS data product generated with Version 7 of the Level 2 algorithm operated by the European Space Agency.The CCl4 zonal means show features typical of long-lived species of anthropogenic origin that are destroyed primarily in the stratosphere, with larger quantities in the troposphere and a monotonic decrease with increasing altitude in the stratosphere. MIPAS CCl4 measurements have been compared with independent measurements from other satellite and balloon-borne remote sounders, showing a good agreement between the different datasets.CCl4 trends are calculated as a function of both latitude and altitude. Negative trends of about −10 to −15 pptv decade−1 (−10 to −30 % decade−1) are found at all latitudes in the upper troposphere–lower stratosphere region, apart from a region in the southern midlatitudes between 50 and 10 hPa where the trend is positive with values around 5–10 pptv decade−1 (15–20 % decade−1). At the lowest altitudes sounded by MIPAS, we find trends consistent with those determined on the basis of long-term ground-based measurements (−10 to −13 pptv decade−1). For higher altitudes, the trend shows a pronounced asymmetry between the Northern and Southern hemispheres, and the magnitude of the decline rate increases with altitude. We use a simplified model assuming tracer–tracer linear correlations to determine CCl4 lifetime in the lower stratosphere. The calculation provides a global average lifetime of 47 (39–61) years, considering CFC-11 as the reference tracer. This value is consistent with the most recent literature result of 44 (36–58) years.

In September–October 2015, El Nino-driven weather conditions led to one of the most intense Indonesian peatland burning events in recent history. Consequently, an unprecedented amount of hydrogen cyanide (HCN) was emitted from Southeast Asia and transported into the upper troposphere and lower stratosphere, which was then transported by the general circulation from the tropics to polar latitudes. By early 2016, the daily mean concentrations of HCN in the lower stratosphere at all latitudes, as measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) instrument, were the largest on record for the region, on the order of 40–90% greater than the climatological mean and ~40% greater than the 2007 El Nino-driven values. By December 2016, levels of polar HCN in the lower stratosphere were still on the order 10–20% greater than the climatological mean. These ACE-FTS measurements are thus vital for interpreting ground-based and nadir satellite measurements of HCN made during 2016 and could be used to help validate tropospheric-stratospheric exchange in climate models.

Near global ozone isotopologue distributions have been determined from infrared solar occultation measurements of the Atmospheric Chemistry Experiment (ACE) satellite mission. ACE measurements are made with a high resolution Fourier transform spectrometer. Annual and seasonal latitudinal fractionation (δ value) distributions of the ozone isotopologues 16O16O18O, 16O18O16O and 16O17O16O were obtained. Asymmetric ozone (16O16O18O) shows higher fractionation compared to symmetric ozone (16O18O16O). The maximum ozone fractionation occurs in the tropical stratosphere as expected from the contribution of photolysis to the enrichment of heavy isotopologues. An enhancement of the heavy ozone isotopologues is also seen in the upper stratosphere of the Antarctic polar vortex.

The Atmospheric Chemistry Experiment (ACE), also called SCISAT, is a Canadian-led small satellite mission for remote sensing of the Earth’s atmosphere. ACE was launched into a low Earth circular orbit by NASA on August 12, 2003 and it continues to function nominally. The ACE instruments are a high spectral resolution (0.02 cm −1 ) Fourier Transform Spectrometer (FTS) operating from 2.2 to 13.3 μm (750–4400 cm −1 ), a spectrophotometer known as Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (MAESTRO) with wavelength coverage of 285–1020 nm and two filtered detector arrays to image the Sun at 0.525 and 1.02 μm. ACE operates in solar occultation mode to provide altitude profiles of temperature, pressure, atmospheric extinction and the volume mixing ratios (VMRs) for several dozen molecules and related isotopologues. This paper presents a mission overview and a summary of selected scientific results.

In this paper, we present an optimized retrieval strategy for carbonyl sulfide (OCS), using Fourier transform infrared (FTIR) solar observations made at the high-altitude Jungfraujoch station in the Swiss Alps. More than 200 lines of the ν3 fundamental band of OCS have been systematically evaluated and we selected 4 microwindows on the basis of objective criteria minimizing the effect of interferences, mainly by solar features, carbon dioxide and water vapor absorption lines, while maximizing the information content. Implementation of this new retrieval strategy provided an extended time series of the OCS abundance spanning the 1995–2015 time period, for the study of the long-term trend and seasonal variation of OCS in the free troposphere and stratosphere. Three distinct periods characterize the evolution of the tropospheric partial columns: a first decreasing period (1995–2002), an intermediate increasing period (2002–2008), and the more recent period (2008–2015) which shows no significant trend. Our FTIR tropospheric and stratospheric time series are compared with new in situ gas chromatography mass spectrometry (GCMS) measurements performed by Empa (Laboratory for Air Pollution/Environmental Technology) at the Jungfraujoch since 2008, and with space-borne solar occultation observations by the ACE-FTS instrument on-board the SCISAT satellite, respectively, and they show good agreement. The OCS signal recorded above Jungfraujoch appears to be closely related to anthropogenic sulfur emissions.

We have developed an approach for retrieving HCFC-142b (CH3CClF2) from ground-based high-resolution infrared solar spectra, using its ν7 band Q branch in the 900–906 cm−1 interval. Interferences by HNO3, CO2 and H2O have to be accounted for. Application of this approach to observations recorded within the framework of long-term monitoring activities carried out at the northern mid-latitude, high-altitude Jungfraujoch station in Switzerland (46.5°N, 8.0°E, 3580 m above sea level) has provided a total column times series spanning the 1989 to mid-2015 time period. A fit to the HCFC-142b daily mean total column time series shows a statistically-significant long-term trend of (1.23±0.08×1013 molec cm−2) per year from 2000 to 2010, at the 2-σ confidence level. This corresponds to a significant atmospheric accumulation of (0.94±0.06) ppt (1 ppt=1/1012) per year for the mean tropospheric mixing ratio, at the 2−σ confidence level. Over the subsequent time period (2010–2014), we note a significant slowing down in the HCFC-142b buildup. Our ground-based FTIR (Fourier Transform Infrared) results are compared with relevant data sets derived from surface in situ measurements at the Mace Head and Jungfraujoch sites of the AGAGE (Advanced Global Atmospheric Gases Experiment) network and from occultation measurements by the ACE-FTS (Atmospheric Chemistry Experiment-Fourier Transform Spectrometer) instrument on-board the SCISAT satellite.

In this paper, we present a new climatology based on, the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) version 3.5 data set from February 2004 to February 2013. This extends the ACE-FTS climatology to include profile information in the mesosphere and carbon-containing species in the upper troposphere and lower stratosphere. Climatologies of 21 species, based on nine years of observations, are calculated, providing the most comprehensive and self-consistent climatology available from limb-viewing satellite measurements. Pressure levels from the upper troposphere to the mesosphere and lower thermosphere are included with similar to 3 to 4 km vertical resolution up to 10(-4) hPa (similar to 105 km). Volume mixing ratio values are filtered prior to the climatology estimation using the ACE-FTS data quality recommendations. The multi-year mean climatology contains zonal mean profiles for monthly and three-monthly (DJF, MAM, JJA, and SON) periods. These are provided with 5-degree spacing in either latitude or equivalent latitude. Also, the local daytime and nighttime distributions are provided separately for nitrogen-containing species, enabling diurnal differences to be investigated. Based on this climatology, examples of typical spatiotemporal patterns for trace gases in the mesosphere and for carbon-containing gases in the upper troposphere and lower stratosphere are discussed. (C) 2016 Elsevier Ltd. All rights reserved.

The ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) instrument on the Canadian SCISAT satellite, which has been in operation for over 12 years, has the capability of deriving stratospheric profiles of many of the NOy (N + NO + NO2+ NO3+ 2 × N2O5+ HNO3+ HNO4+ ClONO2+ BrONO2) species. Version 2.2 of ACE-FTS NO, NO2, HNO3, N2O5, and ClONO2 has previously been validated, and this study compares the most recent version (v3.5) of these five ACE-FTS products to spatially and temporally coincident measurements from other satellite instruments – GOMOS, HALOE, MAESTRO, MIPAS, MLS, OSIRIS, POAM III, SAGE III, SCIAMACHY, SMILES, and SMR. For each ACE-FTS measurement, a photochemical box model was used to simulate the diurnal variations of the NOy species and the ACE-FTS measurements were scaled to the local times of the coincident measurements. The comparisons for all five species show good agreement with correlative satellite measurements. For NO in the altitude range of 25–50 km, ACE-FTS typically agrees with correlative data to within −10 %. Instrument-averaged mean relative differences are approximately −10 % at 30–40 km for NO2, within ±7 % at 8–30 km for HNO3, better than −7 % at 21–34 km for local morning N2O5, and better than −8 % at 21–34 km for ClONO2. Where possible, the variations in the mean differences due to changes in the comparison local time and latitude are also discussed.

We present cross-validation of remote sensing measurements of methane profiles in the Canadian high Arctic. Accurate and precise measurements of methane are essential to understand quantitatively its role in the climate system and in global change. Here, we show a cross-validation between three data sets: two from spaceborne instruments and one from a ground-based instrument. All are Fourier transform spectrometers (FTSs). We consider the Canadian SCISAT Atmospheric Chemistry Experiment (ACE)-FTS, a solar occultation infrared spectrometer operating since 2004, and the thermal infrared band of the Japanese Greenhouse Gases Observing Satellite (GOSAT) Thermal And Near infrared Sensor for carbon Observation (TANSO)-FTS, a nadir/off-nadir scanning FTS instrument operating at solar and terrestrial infrared wavelengths, since 2009. The ground-based instrument is a Bruker 125HR Fourier transform infrared (FTIR) spectrometer, measuring mid-infrared solar absorption spectra at the Polar Environment Atmospheric Research Laboratory (PEARL) Ridge Laboratory at Eureka, Nunavut (80° N, 86° W) since 2006. For each pair of instruments, measurements are collocated within 500 km and 24 h. An additional collocation criterion based on potential vorticity values was found not to significantly affect differences between measurements. Profiles are regridded to a common vertical grid for each comparison set. To account for differing vertical resolutions, ACE-FTS measurements are smoothed to the resolution of either PEARL-FTS or TANSO-FTS, and PEARL-FTS measurements are smoothed to the TANSO-FTS resolution. Differences for each pair are examined in terms of profile and partial columns. During the period considered, the number of collocations for each pair is large enough to obtain a good sample size (from several hundred to tens of thousands depending on pair and configuration). Considering full profiles, the degrees of freedom for signal (DOFS) are between 0.2 and 0.7 for TANSO-FTS and between 1.5 and 3 for PEARL-FTS, while ACE-FTS has considerably more information (roughly 1 DOFS per altitude level). We take partial columns between roughly 5 and 30 km for the ACE-FTS–PEARL-FTS comparison, and between 5 and 10 km for the other pairs. The DOFS for the partial columns are between 1.2 and 2 for PEARL-FTS collocated with ACE-FTS, between 0.1 and 0.5 for PEARL-FTS collocated with TANSO-FTS or for TANSO-FTS collocated with either other instrument, while ACE-FTS has much higher information content. For all pairs, the partial column differences are within ±3 × 1022 molecules cm−2. Expressed as median ± median absolute deviation (expressed in partial column units or as a percentage), these differences are 0.11 ± 9.60 × 1020 molecules cm−2 (0.012 ± 1.018 %) for TANSO-FTS–PEARL-FTS, −2.6 ± 2.6 × 1021 cm−2 (−1.6 ± 1.6 %) for ACE-FTS–PEARL-FTS, and 7.4 ± 6.0 × 1020 molecules cm−2 (0.78 ± 0.64 %) for TANSO-FTS–ACE-FTS. The differences for ACE-FTS–PEARL-FTS and TANSO-FTS–PEARL-FTS partial columns decrease significantly as a function of PEARL partial columns, whereas the range of partial column values for TANSO-FTS–ACE-FTS collocations is too small to draw any conclusion on its dependence on ACE-FTS partial columns.

Nitrous oxide (N2O) is an important anthropogenic greenhouse gas, as well as one of the most significant anthropogenic ozone-depleting substances in the stratosphere. The satellite-based instrument Atmospheric Chemistry Experiment-Fourier Transform Spectrometer has been observing the Earth’s limb since 2004 and derives profiles of N2O volume mixing ratios in the upper troposphere to the lower thermosphere. The resulting climatology shows that N2O is continuously produced in the lower thermosphere via energetic particle precipitation and enhanced N2O is present at all latitudes, during all seasons. The results are consistent with an N2O production source peaking near or above 94 km via low-energy particles, as well as a polar wintertime source near 70 km via medium energy particles. N2O produced in the polar upper atmosphere descends each winter to as far down as ~40 km.

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 analyze 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 inter-comparison 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.

This paper presents an analysis of observations of methane and its two major isotopologues, CH3D and 13CH4, from the Atmospheric Chemistry Experiment (ACE) satellite between 2004 and 2013. Additionally, atmospheric methane chemistry is modeled using the Whole Atmospheric Community Climate Model (WACCM). ACE retrievals of methane extend from 6 km for all isotopologues to 75 km for 12CH4, 35 km for CH3D, and 50 km for 13CH4. While total methane concentrations retrieved from ACE agree well with the model, values of δD–CH4 and δ13C–CH4 show a bias toward higher δ compared to the model and balloon-based measurements. Errors in spectroscopic constants used during the retrieval process are the primary source of this disagreement. Calibrating δD and δ13C from ACE using WACCM in the troposphere gives improved agreement in δD in the stratosphere with the balloon measurements, but values of δ13C still disagree. A model analysis of methane's atmospheric sinks is also performed.

The impact of volcanic eruptions on water vapour in the high-latitude upper troposphere is studied using deseasonalized time series based on observations by the Atmospheric Chemistry Experiment (ACE) water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS). The two eruptions with the greatest impact on the high-latitude upper troposphere during the time frame of this satellite-based remote sensing mission are chosen. The Puyehue–Cordón Caulle volcanic eruption in June 2011 was the most explosive in the past 24 years and is shown to be able to account for the observed (50 ± 12) % increase in water vapour in the southern high-latitude upper troposphere in July 2011 after a minor adjustment for the simultaneous influence of the Antarctic oscillation. Eyjafjallajökull erupted in the spring of 2010, increasing water vapour in the upper troposphere at northern high latitudes significantly for a period of ∼ 1 month. These findings imply that extratropical volcanic eruptions in windy environments can lead to significant perturbations to high-latitude upper tropospheric humidity mostly due to entrainment of lower tropospheric moisture by wind-blown plumes. The Puyehue–Cordón Caulle eruption must be taken into account to properly determine the magnitude of the trend in southern high-latitude upper tropospheric water vapour over the last decade.

The Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer (FTS) has been measuring water vapor and methane in the stratosphere and mesosphere from low Earth orbit since 2004. Recently, substantial increases in water vapor in the upper atmosphere were observed with the MLS and SABER satellite instruments. The main source of water vapor in the upper atmosphere is methane oxidation. ACE-FTS data show substantial water and methane increases, and confirm that the methane increases are too small to explain the water increases. Therefore, changes in the transport of water across the tropical tropopause layer and in atmospheric dynamics are responsible for the positive water trends.

This paper will compare NO2 data from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) with correlative data from the new Stratospheric Aerosol and Gas Experiment III on the International Space Station (SAGE III/ISS).

Recent satellite measurements of a layer of enhanced nitrous oxide (N₂O) in the mesosphere-lower thermosphere (MLT) from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer have suggested an unexpected, minor high-altitude production source. Here we report the development of a mechanism and the first model simulations, which can explain the formation of this MLT N₂O layer. N₂O production occurs primarily via a reaction route involving the excitation of N₂ from secondary electrons. Simulations using the Whole Atmosphere Community Climate Model, with external forcing from the Global Airglow model, quantitatively reproduce the observed vertical, latitudinal, and seasonal N₂O variations. Sensitivity results indicate that photoelectrons are far more important than previously predicted, causing approximately two thirds of global N₂O production in the MLT. Energetic electron precipitation over high latitudes provides the remaining contribution. Solar cycle analysis reveals N₂O enhancements of up to ×2 at solar maximum compared to solar minimum.

This paper will describe Atmospheric Chemistry – Experiment Fourier Transform Spectrometer (ACE-FTS) N2O measurements in the middle atmosphere along with its production mechanisms and long-term variation. Comparisons with model N2O simulations will also be discussed.

This paper will describe the current validation results for the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) with a focus on long-term validation efforts and overall mission status for this instrument.

The primary instrument on the Greenhouse gases Observing SATellite (GOSAT) is the Thermal And Near infrared Sensor for carbon Observations (TANSO) Fourier Transform Spectrometer (FTS). TANSO-FTS uses three short-wave infrared (SWIR) bands to retrieve total columns of CO2 and CH4 along its optical line-of-sight, and one thermal infrared (TIR) channel to retrieve vertical profiles of CO2 and CH4 volume mixing ratios (VMRs) in the troposphere. We examine version 1 of the TANSO-FTS TIR CH4 product by comparing co-located CH4 VMR vertical profiles from two other remote sensing FTS systems: the Canadian Space Agency's Atmospheric Chemistry Experiment-FTS (ACE-FTS) on SCISAT (version 3.5), and the European Space Agency's Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat (ESA ML2PP version 6 and IMK-IAA reduced-resolution version V5R_CH4_224/225), as well as 16 ground stations with the Network for the Detection of Atmospheric Composition Change (NDACC). This work follows an initial inter-comparison study over the Arctic, which incorporated a ground-based FTS at the Polar Environment Atmospheric Research Laboratory (PEARL) at Eureka, Canada, and focuses on tropospheric and lower-stratospheric measurements made at middle and tropical latitudes between 2009 to 2013 (mid 2012 for MIPAS). For comparison, vertical profiles from all instruments are interpolated onto a common pressure grid, and the ACE-FTS, MIPAS, and NDACC vertical profiles are smoothed using the TANSO-FTS averaging kernels. We present zonally-averaged mean CH4 differences between each instrument and TANSO-FTS with and without smoothing, examine their information content, sensitive altitude range, correlation, a priori dependence, and the variability within each data set. Partial columns are calculated from the VMR vertical profiles, and their correlations are examined. We find that the TANSO-FTS vertical profiles agree with the ACE-FTS and both MIPAS retrievals' vertical profiles within 4 % below 15 km when smoothing is applied to the profiles from instruments with finer vertical resolution, but that the relative differences can increase to on the order of 25 % when no smoothing is applied. Computed partial columns are tightly correlated for each pair of data sets. We investigated whether the difference between TANSO-FTS and other CH4 VMR data products varies with latitude. Our study reveals a small dependence of around 0.1 % per ten degrees latitude, with smaller differences over the equator, and greater differences towards the poles.

Atmospheric emissions of Carbon tetrachloride CCl4 are regulated by the Montreal Protocol due to its role as a strong ozone-depleting substance. The molecule has been the subject of recent increased interest as a consequence of the so called ``mystery of CCl4,'' the discrepancy between atmospheric observations and reported production and consumption. Surface measurements of CCl4 atmospheric concentrations have declined at a rate almost three times smaller than its lifetime-limited rate, suggesting persistent atmospheric emissions despite the ban. In this paper, we study CCl4 vertical and zonal distributions in the upper troposphere and lower stratosphere (including the photolytic loss region, 70–20 hPa), its trend, and its stratospheric lifetime using measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), which operated onboard the ENVISAT satellite from 2002 to 2012. Specifically, we use the MIPAS data product generated with Version 7 of the Level 2 algorithm operated by the European Space Agency. The CCl4 zonal means show features typical of long-lived species of anthropogenic origin that are destroyed primarily in the stratosphere, with larger quantities in the troposphere and a monotonic decrease with increasing altitude in the stratosphere. In the troposphere, the largest concentrations are observed at the latitudes of major industrial countries (20/50°N). The good agreement we find between MIPAS CCl4 and independent measurements from other satellite and balloon-borne remote sounders proves the reliability of the MIPAS dataset. CCl4 trends are calculated as a function of both latitude and altitude. Negative trends are found at all latitudes in the upper-troposphere / lower-stratosphere region, apart from a region in the Southern mid-latitudes between 50 and 10 hPa where the trend is positive. At the lowest altitudes sounded by MIPAS, we find trends consistent with those determined on the basis of long-term ground-based measurements. For higher altitudes, the trend shows a pronounced asymmetry between Northern and Southern Hemispheres, and the magnitude of the decline rate increases with altitude. At 50 hPa the decline is about 30–35 %/decade, close to the lifetime-limited trend. We use a simplified model assuming tracer-tracer linear correlations to determine CCl4 lifetime in the lower stratosphere. The calculation provides a global average lifetime of 46(38–60) years considering CFC-11 as the reference tracer. This value is consistent with the most recent literature result of 44(36–58) years.

MIPAS thermal limb emission measurements were used to derive vertically resolved profiles of carbon tetrachloride (CCl4). Level-1b data versions MIPAS/5.02 to MIPAS/5.06 were converted into profiles using the level-2 processor developed at Karlsruhe Institute of Technology (KIT) Institute of Meteorology and Climate Research (IMK) and Consejo Superior de Investigaciones Científicas (CSIC), Instituto de Astrofísica de Andalucía (IAA). Consideration of peroxyacetyl nitrate (PAN) as interfering species, which is jointly retrieved and CO2 line mixing, was found to be crucial for reliable retrievals. Parts of the CO2 Q-branch region that overlap with the CCl4 signature were omitted, since large residuals were still found even though line mixing was considered in the forward model. However, the omitted spectral region could be narrowed considerably when line mixing was a44 volume mixing ratios. In general, latitude-altitude cross-section show the expected CCl4 features with highest values of around 90 pptv at altitudes at and below the tropical tropopause and values decreasing with altitude and latitude due to stratospheric decomposition. Other patterns, such as subsidence in the polar vortex during winter and early spring, are also visible in the distributions. The decline in CCl4 abundance during the MIPAS Envisat measurement period (July 2002 to April 2012) is clearly reflected in the retrieved distributions.

An analysis of the Atmospheric Chemistry Experiment (ACE) infrared Fourier transform spectrometer (FTS) spectra for signatures of Polar Mesospheric Clouds (PMCs) has been carried out by looking for the O-H vibrational mode at ≈ 3240 cm − 1 . PMCs are thought to be indicators of climate change in the mesosphere and have been found to be increasing in recent years. Additionally, there are a number of open questions about the microphysics of the clouds, and their physical properties such as temperature, density, and particle shape and size. ACE has access to the entire infrared spectrum, potentially providing more accurate retrievals of these parameters. Using the T-matrix scattering code, we have made fits to the 3 micron ACE-FTS spectra. The ACE data set yielded 1762 unique occultations; after accounting for false positives, 955 occultations were left. We assumed oblate spheroids with a fixed effective radius of 40 nm and a nominal cloud size of 200 km, and obtained reasonable distributions for temperature, axial ratio and particle density. We expect that the methods presented here will allow a new routine ACE PMC data product to be developed.

The Montreal Protocol banned the production of major ozone depleting substances such as chlorofluorocarbons (CFCs) to protect the Earth’s ozone layer. The resulting increased production and emissions of CFC-replacement hydrofluorocarbons (HFCs) has caused a dramatic increase in their atmospheric abundances. Although these HFCs do not contribute directly to the depletion of the ozone layer because they contain no chlorine, they are powerful greenhouse gases with large global warming potentials. In January 2019, the Kigali Amendment to the Montreal Protocol came into force to phase out long-lived HFCs. The two most abundant HFCs in the atmosphere, HFC-134a (CF3CH2F) and HFC-23 (CHF3), are measured from orbit by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). These measurements will be useful for monitoring the Kigali Amendment to the Montreal Protocol. Analysis of the ACE-FTS measurements provides near-global distributions and confirms the rapid increase in HFC-134a (4.9 ± 0.1 ppt per year) and HFC-23 (0.75 ± 0.02 ppt per year) volume mixing ratios (VMRs).

The Montreal Protocol has banned the production of long-lived halogen-containing molecules such as chlorofluorocarbons (CFCs) that are responsible for the widespread destruction of stratospheric ozone. Sixteen halogen-containing trace gases (CCl4, CF4, CFC-11, CFC-12, CFC-113, CH3Cl, ClONO2, COCl2, COClF, COF2, HCFC-22, HCFC-141b, HCFC-142b, HCl, HF, SF6) are observed globally by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) which measures atmospheric spectra via solar occultation from low-Earth orbit. The ACE satellite was launched in August 2003 and continues to operate with minimal degradation to this day. ACE is uniquely able to provide global long term trends of the concentrations of many atmospheric constituents. In this work we present time series trends and altitude-latitude distributions of halogen-containing trace gases. For 12 molecules the altitude-latitude distributions are reliable, but for CF4, CFC-113, HCFC-141b and HCFC-142b the distributions are anomalous likely because of spectroscopic interference in the retrieval. These 16 species can be categorized as source gases such as CFCs emitted at the surface and product gases such as HCl, HF and ClONO2 that are formed by chemical reactions from the source gases. Many of these substances deplete stratospheric ozone and are potent greenhouse gases that contribute to climate change.

The Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) has been measuring atmospheric composition by solar occultation from low Earth orbit since 2004. A new version (4.0) of ACE-FTS processing has added low altitude CO2 as a routine data product. ACE provides a near global data set of altitude profiles of CO2 volume mixing ratios (VMRs) on a 1 km grid from 5 to 18 km. We provide an initial evaluation of these data using occultations from the month of May for 2004–2017 in the 55°–70°S latitude range. Comparisons are made with ground-based measurements at Macquarie Island, the South Pole, the CarbonTracker 2017 model and G. Toon's empirical model. Agreement for trends is good, but ACE-FTS VMRs have a low bias at 5.5 and 6.5 km in altitude.

Fluorine-containing species can be extremely effective atmospheric greenhouse gases. We present fluorine budgets using organic and inorganic species retrieved by the ACE-FTS satellite instrument supplemented with output from the SLIMCAT 3-D chemical transport model. The budgets are calculated between 2004 and 2009 for a number of latitude bands: 70–30° N, 30–00° N, 00° N–30° S, and 30–70° S. At lower altitudes total fluorine profiles are dominated by the contribution from CFC-12, up to an altitude of 20 km in the extra-tropics and 29 km in the tropics; above these altitudes the profiles are dominated by hydrogen fluoride (HF). Our data show that total fluorine profiles at all locations have a negative slope with altitude, providing evidence that overall fluorine emissions (measured by their F content) have been increasing with time. Total stratospheric fluorine is increasing at a similar rate in the tropics: 32.5 ± 4.9 ppt yr−1 (1.31 ± 0.20% per year) in the Northern Hemisphere (NH) and 29.8 ± 5.3 ppt yr−1 (1.21 ± 0.22% per year) in the Southern Hemisphere (SH). Extra-tropical total stratospheric fluorine is also increasing at a similar rate in both the NH and SH: 28.3 ± 2.7 ppt per year (1.12 ± 0.11% per year) in the NH and 24.3 ± 3.1 ppt per year (0.96 ± 0.12% per year) in the SH. The calculation of radiative efficiency-weighted total fluorine allows the changes in radiative forcing between 2004 and 2009 to be calculated. These results show an increase in radiative forcing of between 0.23 ± 0.11% per year and 0.45 ± 0.11% per year, due to the increase in fluorine-containing species during this time. The decreasing trends in the mixing ratios of halons and chlorofluorocarbons (CFCs), due to their prohibition under the Montreal Protocol, have suppressed an increase in total fluorine caused by increasing mixing ratios of hydrofluorocarbons (HFCs). This has reduced the impact of fluorine-containing species on global warming.

We observed ozone (O3) in the vertical region between 250 and 0.0005 hPa (~ 12–96 km) using the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on the Japanese Experiment Module (JEM) of the International Space Station (ISS) between 12 October 2009 and 21 April 2010. The new 4 K superconducting heterodyne receiver technology of SMILES allowed us to obtain a one order of magnitude better signal-to-noise ratio for the O3 line observation compared to past spaceborne microwave instruments. The non-sun-synchronous orbit of the ISS allowed us to observe O3 at various local times. We assessed the quality of the vertical profiles of O3 in the 100–0.001 hPa (~ 16–90 km) region for the SMILES NICT Level 2 product version 2.1.5. The evaluation is based on four components: error analysis; internal comparisons of observations targeting three different instrumental setups for the same O3 625.371 GHz transition; internal comparisons of two different retrieval algorithms; and external comparisons for various local times with ozonesonde, satellite and balloon observations (ENVISAT/MIPAS, SCISAT/ACE-FTS, Odin/OSIRIS, Odin/SMR, Aura/MLS, TELIS). SMILES O3 data have an estimated absolute accuracy of better than 0.3 ppmv (3%) with a vertical resolution of 3–4 km over the 60 to 8 hPa range. The random error for a single measurement is better than the estimated systematic error, being less than 1, 2, and 7%, in the 40–1, 80–0.1, and 100–0.004 hPa pressure regions, respectively. SMILES O3 abundance was 10–20% lower than all other satellite measurements at 8–0.1 hPa due to an error arising from uncertainties of the tangent point information and the gain calibration for the intensity of the spectrum. SMILES O3 from observation frequency Band-B had better accuracy than that from Band-A. A two month period is required to accumulate measurements covering 24 h in local time of O3 profile. However such a dataset can also contain variation due to dynamical, seasonal, and latitudinal effects.

[1] Satellite measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) are used to examine the global, seasonal variations of several hydrocarbons, including carbon monoxide (CO), ethane (C2H6), acetylene (C2H2), and hydrogen cyanide (HCN). We focus on quantifying large-scale seasonal behavior from the middle troposphere to the stratosphere, particularly in the tropics, and furthermore make detailed comparisons with the Whole Atmosphere Community Climate Model (WACCM) chemistry climate model (incorporating tropospheric photochemistry, time-varying hydrocarbon emissions, and meteorological fields nudged from reanalysis). Comparisons with Microwave Limb Sounder (MLS) measurements of CO are also included to understand sampling limitations of the ACE-FTS data and biases among observational data sets. Results show similar overall variability for CO, C2H6, and C2H2, with a semiannual cycle in the tropical upper troposphere related to seasonallyvarying sources and deep tropical convection, plus a maximum during Northern Hemisphere summer tied to the Asian monsoon anticyclone. These species also reveal a strong annual cycle above the tropical tropopause, tied to annual variations in the upward branch of Brewer-Dobson circulation. HCN reveals substantial differences from the other species, due to a longer photochemical lifetime and a chemical sink associated with ocean surface contact, which produces a minimum in the tropical upper troposphere not observed in the other species. For HCN, transport to the stratosphere occurs primarily through the Asian summer monsoon anticyclone. Overall, the WACCM simulation is able to reproduce most of the large-scale features observed in the ACE-FTS data, suggesting a reasonable simulation of sources and large-scale transport. The model is too low in the Southern Hemisphere subtropics during Austral spring, which indicates underestimate of biomass burning emissions and/or insufficient vertical transport in the model.

We present measurements from the Water Vapor Millimeter-wave Spectrometer (WVMS) instruments at Table Mountain, California (34.4°N, 242.3°E), and Mauna Loa, Hawaii (19.5°N, 204.4°E), and highlight the extended altitude range of the measurements at these sites, which now provide measurements down to 26 km. We show that this extended altitude range has been acquired without disturbing the existing long-term WVMS data set at Mauna Loa. Validation of the successful transition is provided by comparing WVMS measurements with coincident satellite measurements from the Aura Microwave Limb Sounder (MLS), the Atmospheric Chemistry Experiment, and the Michelson Interferometer for Passive Atmospheric Sounding. At the lowest altitudes where WVMS measurements are possible, we also compare with frost-point hygrometer balloon measurements. The water vapor mixing ratios measured at 50 km over Mauna Loa are the highest ever reported in the WVMS (since 1996) or MLS (since 2004) time series. Particularly encouraging for the new 26 km WVMS measurements is that they indicate an increase between 2010 and 2011 that is comparable to that observed by other instruments. This shows that these measurements are sensitive to variations at this altitude and that the instrumental baseline remains stable.

A near global distribution of hydrogen peroxide (H2O2) in the mid- to upper troposphere and low to mid-stratosphere was obtained by the Atmospheric Chemistry Experiment (ACE) satellite. The data show that hydrogen peroxide exhibits both a seasonal and diurnal cycle with high variability in the upper troposphere. ACE data also show the influence of photochemistry on sunrise and sunset hydrogen peroxide distributions. The tropospheric hydrogen peroxide distribution was compared with output from the three-dimensional chemical transport model GEOS-Chem. The GEOS-Chem model is in good general agreement with ACE for hydrogen peroxide, capturing the main features observed including the diurnal and seasonal variation; however volume mixing ratios (VMRs) for the model are consistently greater than those of ACE.

Doppler-limited rovibrational absorption spectra of the A 3 Π 1 u ← X 1 Σ g + electronic transition of Br2 are measured in the 12 072–14 249 cm−1 region by a tone burst modulation method using a Ti:sapphire ring laser. P-, Q-, and R-branch lines belonging to the v′ ← v″ = (2–16) ← (2–8) bands of 79,79Br2 and 79,81Br2, and the v′ ← v″ = (2–5) ← 6 bands of 81,81Br2 are observed and assigned. Accurate analytic potential energy functions for the A3Π1u and X 1 Σ g + states are determined from a combined-isotopologue direct-potential-fit analysis of these data together with all other available high quality data for the A and X states. This work also yields a slightly improved ground-state well depth D e ( X ) = 16056.875 ( 2 ) cm - 1 and dissociation energy D 0 ( X ) = 15894.495 ( 2 ) cm - 1 for 79,79Br2, and shows that the isotope shift of the A–X electronic transition energy T e 81 , 81 – T e 79 , 79 = - 0.016 ( 3 ) cm - 1 is likely mainly due to the isotopologue dependence of theX-state well depth.

Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74 % of total), but a reported 10 % uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9 % of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17 % of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year−1, the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year−1. Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks.

Changes of atmospheric methane (CH4) since 2005 have been evaluated using Fourier Transform Infrared (FTIR) solar observations performed at ten ground-based sites, all members of the Network for Detection of Atmospheric Composition Change (NDACC). From this, we find an increase of atmospheric methane total columns that amounts to 0.31 ± 0.03 % year−1 (2-sigma level of uncertainty) for the 2005–2014 period. Comparisons with in situ methane measurements at both local and global scales show good agreement. We used the GEOS-Chem Chemical Transport Model tagged simulation that accounts for the contribution of each emission source and one sink in the total methane, simulated over the 2005–2012 time period and based on emissions inventories and transport. After regridding according to NDACC vertical layering using a conservative regridding scheme and smoothing by convolving with respective FTIR seasonal averaging kernels, the GEOS-Chem simulation shows an increase of atmospheric methane of 0.35 ± 0.03 % year−1 between 2005 and 2012, which is in agreement with NDACC measurements over the same time period (0.30 ± 0.04 % year−1, averaged over ten stations). Analysis of the GEOS-Chem tagged simulation allows us to quantify the contribution of each tracer to the global methane change since 2005. We find that natural sources such as wetlands and biomass burning contribute to the inter-annual variability of methane. However, anthropogenic emissions such as coal mining, and gas and oil transport and exploration, which are mainly emitted in the Northern Hemisphere and act as secondary contributors to the global budget of methane, have played a major role in the increase of atmospheric methane observed since 2005. Based on the GEOS-Chem tagged simulation, we discuss possible cause(s) for the increase of methane since 2005, which is still unexplained.

The ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) instrument on the Canadian SCISAT satellite, which has been in operation for over 12 years, has the capability of deriving stratospheric profiles of many of the NOy (NO + NO2 + NO3 + 2 × N2O5 + HNO3 + HNO4 + ClONO2 + BrONO2) species. Version 2.2 of ACE-FTS NO, NO2, HNO3, N2O5, and ClONO2 have previously been validated, and this study compares the most recent version (v3.5) of these five ACE-FTS products to spatially and temporally coincident measurements from other satellite instruments–GOMOS, HALOE, MAESTRO, MIPAS, MLS, OSIRIS, POAM III, SAGE III, SCIAMACHY, SMILES, and SMR. For each ACE-FTS measurement, a photochemical box model was used to simulate the diurnal variations of the NOy species and the ACE-FTS measurements were scaled to the local times of the coincident measurements. The comparisons for all five species show good agreement with correlative satellite measurements. For NO in the altitude range of 25–50 km, the instrument-averaged mean relative differences are on the order of 0 to −10 %. They are approximately −10 % at 30–40 km for NO2, they are within ±7 % at 8–30 km for HNO3, they are better than −7% at 21–34 km for local morning N2O5, and better than −8 % at 21–34 km for ClONO2. Where possible, the variations in the mean differences due to changes in the comparison local time and latitude are also discussed.

The distributions of the four most abundant isotopologues and isotopomers (N2O, 15NNO, N15NO, and NN18O) of nitrous oxide have been measured in the Earth's stratosphere by infrared remote sensing with the Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer. These satellite observations have provided a near global picture of N2O isotopic fractionation. The relative abundances of the heavier species increase with altitude and with latitude in the stratosphere as the air becomes older. The heavy isotopologues are enriched by 20-30% in the upper stratosphere and even more over the poles. These observations are in general agreement with model predictions made with the Whole Atmosphere Community Climate Model (WACCM). A detailed 3-D chemical transport model is needed to account for the global isotopic distributions of N2O, and to infer sources and sinks.

The changes in the atmospheric concentration of 16 halogenated gases in the atmosphere have been determined using measurements made by the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS). ACE-FTS has been used to measure the change in concentration between 2004 and 2010 of CCl 4 , CF 4 , CCl 3 F (CFC-11), CCl 2 F 2 (CFC-12), C 2 Cl 3 F 3 (CFC-113), CH 3 Cl, ClONO 2 , COF 2 , COCl 2 , COClF, CHF 2 Cl (HCFC-22), CH 3 CCl 2 F (HCFC-141b), CH 3 CClF 2 (HCFC-142b), HCl, HF and SF 6 between 30°N and 30°S. ACE-FTS measurements were compared to surface measurements made by the AGAGE network and output from the SLIMCAT three-dimensional (3-D) chemical transport model, which is constrained by similar surface data. ACE-FTS measurements of CFCs show declining trends which agree with both AGAGE and SLIMCAT values. There are problems with the ACE-FTS retrievals of CFC-113 and HCFCs, with work currently ongoing to correct these problems. At lower altitudes the volume mixing ratio (VMR) of these species increase with altitude. This is due to problems with the retrievals at high beta angle (the angle between the orbital plane and the Earth–Sun vector). Although some of the retrievals have problems, we are confident that the trends are generally reliable. The concentrations of HCFCs appear to be increasing with ACE-FTS, SLIMCAT and AGAGE all showing positive trends. ACE-FTS measurements of the decomposition products (COFCl and COCl 2 ) do not show any significant trends. SLIMCAT data show a negative trend for COFCl which corresponds to the decrease in CFC-11, its assumed major source, during this time. COF 2 measurements from ACE-FTS show an increasing trend, while SLIMCAT shows a decreasing trend again linked to its assumed production from CFCs. ClONO 2 is highly photosensitive, thus the ACE-FTS occultations have been divided into local morning and evening occultations. Evening measurements of ClONO 2 show a decreasing trend in VMR, while morning measurements show an increasing trend. The reason for this difference is not understood at this time. The SLIMCAT output used in this study was not saved as local sunrise and sunset: therefore, only 24 h mean fields are available for ClONO 2 . These SLIMCAT data show a decreasing trend. SLIMCAT and ACE-FTS both show an increasing trend in the VMR of HF and a decreasing trend in the VMR of HCl. These results illustrate the success of the Montreal Protocol in reducing ozone depleting substances. The reduction in anthropogenic chlorine emissions has led to a decrease in the VMR of stratospheric HCl. The replacement of CFCs with HCFCs has led to an increase in the VMR of HF in the stratosphere. As chlorine-containing compounds continue to be phased out and replaced by fluorine-containing molecules, it is likely that total atmospheric fluorine will continue increasing in the near future.