Satellite observations of stratospheric hydrogen fluoride and comparisons with SLIMCAT calculations

The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Many of these fluorine-containing species deplete stratospheric ozone and are regulated by the Montreal Protocol. Once in the atmosphere they slowly degrade, ultimately leading to the formation of hydrogen fluoride (HF), the dominant reservoir of stratospheric fluorine due to its extreme stability. Monitoring the growth of stratospheric HF is therefore an important marker for the success of the Montreal Protocol. We report the comparison of global distributions and trends of HF measured in the Earth's atmosphere by the satellite remote-sensing instruments ACE-FTS (Atmospheric Chemistry Experiment Fourier transform spectrometer), which has been recording atmospheric spectra since 2004, and HALOE (HALogen Occultation Experiment), which recorded atmospheric spectra between 1991 and 2005, with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model. In general the agreement between observation and model is good, although the ACE-FTS measurements are biased high by ~10% relative to HALOE. The observed global HF trends reveal a substantial slowing down in the rate of increase of HF since the 1990s: 4.97±0.12%year-1 (1991-1997; HALOE), 1.12±0.08%year-1 (1998-2005; HALOE), and 0.52±0.03%year-1 (2004-2012; ACE-FTS). In comparison, SLIMCAT calculates trends of 4.01, 1.10, and 0.48%year-1, respectively, for the same periods; the agreement is very good for all but the earlier of the two HALOE periods. Furthermore, the observations reveal variations in the HF trends with latitude and altitude; for example, between 2004 and 2012 HF actually decreased in the Southern Hemisphere below 35km. An additional SLIMCAT simulation with repeating meteorology for the year 2000 produces much cleaner trends in HF with minimal variations with latitude and altitude. Therefore, the variations with latitude and altitude in the observed HF trends are due to variability in stratospheric dynamics on the timescale of a few years. Overall, the agreement between observation and model points towards the ongoing success of the Montreal Protocol and the usefulness of HF as a metric for stratospheric fluorine

Constraints on inorganic gaseous iodine in the tropical upper troposphere and stratosphere inferred from balloon-borne solar occultation observations

We report upper limits of IO and OIO in the tropical upper troposphere and stratosphere inferred from solar occultation spectra recorded by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy) payload during two stratospheric balloon flights from a station in Northern Brazil (5.1°S, 42.9° W). In the tropical upper troposphere and lower stratosphere, upper limits for both, IO and OIO, are below 0.1 ppt. Photochemical modelling is used to estimate the compatible upper limits for the total gaseous inorganic iodine burden (Iy) amounting to 0.09 to 0.16 (+0.10/-0.04) ppt in the tropical lower stratosphere (21.0 km to 16.5 km) and 0.17 to 0.35 (+0.20/-0.08) ppt in the tropical upper troposphere (16.5 km to 13.5 km). In the middle stratosphere, upper limits increase with altitude as sampling sensitivity decreases. Our findings imply that the amount of gaseous iodine transported into the stratosphere through the tropical tropopause layer is small. Thus, iodine-mediated ozone loss plays a minor role for contemporary stratospheric photochemistry but might become significant in the future if source gas emissions or injection efficiency into the upper atmosphere are enhanced. However, photochemical modelling uncertainties are large and iodine might be transported into the stratosphere in particulate form

CH4 concentrations over the Amazon from GOSAT consistent with in situ vertical profile data

The Amazon Basin contains large wetland ecosystems which are important sources of methane (CH4). Spaceborne observations of atmospheric CH4 can provide constraints on emissions from these remote ecosystems, but lack of validation precludes robust estimates. We present the first validation of CH4 columns in the Amazon from the Greenhouse gases Observing SATellite (GOSAT) using aircraft measurements of CH4 over five sites across the Amazon Basin. These aircraft profiles, combined with stratospheric results from the TOMCAT chemical transport model, are vertically integrated allowing direct comparison to the GOSAT XCH4 measurements (the column-averaged dry air mole fraction of CH4). The measurements agree within uncertainties or show no significant difference at three of the aircraft sites, with differences ranging from -1.9 ppb to 6.6 ppb, while at two sites GOSAT XCH4 is shown to be slightly higher than aircraft measurements, by 8.1 ppb and 9.7 ppb. The seasonality in XCH4 seen by the aircraft profiles is also well captured (correlation coefficients from 0.61 to 0.90). GOSAT observes elevated concentrations in the northwest corner of South America in the dry season and enhanced concentrations elsewhere in the Amazon Basin in the wet season, with the strongest seasonal differences coinciding with regions in Bolivia known to contain large wetlands. Our results are encouraging evidence that these GOSAT CH4 columns are generally in good agreement with in situ measurements, and understanding the magnitude of any remaining biases between the two will allow more confidence in the application of XCH4 to constrain Amazonian CH4 fluxes