Thomas Blumenstock

Long‐term trends of inorganic chlorine from ground‐based infrared solar spectra: Past increases and evidence for stabilization

Long-term time series of hydrogen chloride (HCl) and chlorine nitrate (ClONO2) total column abundances has been retrieved from high spectral resolution ground-based solar absorption spectra recorded with infrared Fourier transform spectrometers at nine NDSC (Network for the Detection of Stratospheric Change) sites in both Northern and Southern Hemispheres. The data sets span up to 24 years and most extend until the end of 2001. The time series of Cl-y (defined here as the sum of the HCl and ClONO2 columns) from the three locations with the longest time-span records show rapid increases until the early 1990s superimposed on marked day-to-day, seasonal and inter-annual variability. Subsequently, the buildup in Cl-y slows and reaches a broad plateau after 1996, also characterized by variability. A similar time evolution is also found in the total chlorine concentration at 55 km altitude derived from Halogen Occultation Experiment (HALOE) global observations since 1991. The stabilization of inorganic chlorine observed in both the total columns and at 55 km altitude indicates that the near-global 1993 organic chlorine (CCly) peak at the Earths surface has now propagated over a broad altitude range in the upper atmosphere, though the time lag is difficult to quantify precisely from the current data sets, due to variability. We compare the three longest measured time series with two-dimensional model calculations extending from 1977 to 2010, based on a halocarbon scenario that assumes past measured trends and a realistic extrapolation into the future. The model predicts broad Cl-y maxima consistent with the long-term observations, followed by a slow Cl-y decline reaching 12-14% relative to the peak by 2010. The data reported here confirm the effectiveness of the Montreal Protocol and its Amendments and Adjustments in progressively phasing out the major man-related perturbations of the stratospheric ozone layer, in particular, the anthropogenic chlorine-bearing source gases. (Less)

Recent Northern Hemisphere stratospheric HCl increase due to atmospheric circulation changes

The abundance of chlorine in the Earth’s atmosphere increased considerably during the 1970s to 1990s, following large emissions of anthropogenic long-lived chlorine-containing source gases, notably the chlorofluorocarbons. The chemical inertness of chlorofluorocarbons allows their transport and mixing throughout the troposphere on a global scale, before they reach the stratosphere where they release chlorine atoms that cause ozone depletion. The large ozone loss over Antarctica was the key observation that stimulated the definition and signing in 1987 of the Montreal Protocol, an international treaty establishing a schedule to reduce the production of the major chlorine- and bromine-containing halocarbons. Owing to its implementation, the near-surface total chlorine concentration showed a maximum in 1993, followed by a decrease of half a per cent to one per cent per year, in line with expectations. Remote-sensing data have revealed a peak in stratospheric chlorine after 1996, then a decrease of close to one per cent per year, in agreement with the surface observations of the chlorine source gases and model calculations. Here we present ground-based and satellite data that show a recent and significant increase, at the 2σ level, in hydrogen chloride (HCl), the main stratospheric chlorine reservoir, starting around 2007 in the lower stratosphere of the Northern Hemisphere, in contrast with the ongoing monotonic decrease of near-surface source gases. Using model simulations, we attribute this trend anomaly to a slowdown in the Northern Hemisphere atmospheric circulation, occurring over several consecutive years, transporting more aged air to the lower stratosphere, and characterized by a larger relative conversion of source gases to HCl. This short-term dynamical variability will also affect other stratospheric tracers and needs to be accounted for when studying the evolution of the stratospheric ozone layer.

Camtracker: a new camera controlled high precision solar tracker system for FTIR-spectrometers

Abstract. A new system to very precisely couple radiation of a moving source into a Fourier Transform Infrared (FTIR) Spectrometer is presented. The Camtracker consists of a homemade altazimuthal solar tracker, a digital camera and a homemade program to process the camera data and to control the motion of the tracker. The key idea is to evaluate the image of the radiation source on the entrance field stop of the spectrometer. We prove that the system reaches tracking accuracies of about 10 arc s for a ground-based solar absorption FTIR spectrometer, which is significantly better than current solar trackers. Moreover, due to the incorporation of a camera, the new system allows to document residual pointing errors and to point onto the solar disk center even in case of variable intensity distributions across the source due to cirrus or haze.

On the use of HF as a reference for the comparison of stratospheric observations and models

Hydrogen fluoride (HF) is often used as a simple reference for other column observations of chemically active stratospheric species. However, seasonal and shorter timescale variations in column HF make its use as a reference more complicated. In this paper we characterize the expected magnitude of these variations in HF, and variations of ratio quantities involving HF, using a two-dimensional (2-D) photochemical model and two versions of a three-dimensional (3-D) transport model. The 2-D model predicts that the column ratios HNO3/HF and HCl/HF increase from midlatitudes to the tropics, although this is very sensitive to HCl and HNO3 abundances in the tropical upper troposphere. Seasonal variations in vertical motion modifys the predicted ratios; for example, wintertime descent at high latitudes decreases HCl/HF. The ratio HNO3/HF at high latitudes is strongly modified by seasonal variations in the chemical partitioning of the odd nitrogen (NOy) species. We compare these model predictions with ground-based Fourier transform infrared spectroscopy (FTIR) observations of HF along with HCl, ClONO2 and HNO3 obtained at eight northern hemisphere sites between October 1994 and July 1995. We investigate quantitatively how HF can be used as a tracer to follow the evolution of observations at a single station and to intercompare results from different stations or with photochemical models. The magnitude of the 3-D model HF column agrees well with the observations, except on some occasions at high latitudes, giving indirect support for the important role of COF2 in the stratospheric inorganic fluorine budget. The observed day-to-day variability in the column ratios HCl/HF and HNO3/HF is much larger at high latitudes. This variability is reproduced in the 3-D models and is due to horizontal motion. Short timescale vertical displacement of the species profiles is estimated to have a small effect on the column ratios. In particular, we analyze the usefulness of the observed column ratio (ClONO2 + HCl)/HF as an indicator for chlorine activation. Current measurement uncertainties limit the degree of activation which can be unambiguously detected using this observed quantity, but we can determine that chlorine-activated air was observed above Aberdeen (58°N) on 6 days in late January 1995.

First results of ground‐based FTIR measurements of atmospheric trace gases in north Sweden and Greenland during EASOE

Zenith column amounts of N2O, CH4, CFC-12, O3, HNO3, ClONO2, HCl, and HF were measured by ground-based FTIR spectrometers at Kiruna in November 1991 and from January to March 1992, and in January and March 1992 in Sondre Stromfjord, Greenland. They were correlated to the dynamical situation of the stratosphere and interpreted in terms of chemical processes, with respect to the position of the vortex, the stratospheric temperatures, and the trajectories of the air masses for the last ten days. One of the most remarkable results is the increasing ClONO2 burden from the end of January to mid-March, reaching the extremely high value of 7.2 × 1015 molec./cm².

Column amounts of trace gases derived from ground‐based measurements with MIPAS during CHEOPS III

Infrared solar absorption spectra of the atmosphere were taken during the CHEOPS III campaign in Esrange, Sweden in January and February 1990. The MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) instrument used has an unapodized spectral resolution of 0.015 cm{sup {minus}1}. Spectra were analyzed by means of the SCAIS (Simulation Code for Atmospheric Infrared Spectra) level-by-level and line-by-line algorithm for radiative transfer through the atmosphere. The time series of the retrieved zenith column amounts of O{sub 3}, H{sub 2}O, CH{sub 4}, N{sub 2}O, HNO{sub 3}, NO{sub 2}, HCl, and HF are presented. The stratospheric HCl/HF ratio of 1.3 at the beginning of February, 1990 points towards the conversion of a considerable potion of gaseous HCl to other chemical or physical forms in the stratosphere in this period. A significant change in the HCl column amount between February 4, 1990 and February 8, 1990 was found; this can be correlated with a stratospheric warming between these two dates. From January 27, 1990 to February 11, 1990 the derived upper limits of NO{sub 2} abundances were low ({le} 1.2 {times} 10{sup 15} molecules/cm{sup 2}), whereas the column amounts of HNO{sub 3} were very high with 2.9 {times} 10{sup 16} molecules/cm{sup 2}.

Mountain polar stratospheric cloud measurements by Ground Based FTIR Solar Absorption Spectroscopy

An analysis of mountain polar stratospheric cloud observations by solar absorption FTIR from Kiruna/Sweden was performed and compared with co-located airborne lidar measurements. The infrared cloud spectral signature and optical depth indicated water ice particles compatible with the high backscatter and depolarization ratio of the lidar signal. Retrieval of mean particle properties from the FTIR spectrum depend on the assumed width of the particle size distribution and range from 2.0 to 1.1 µm radius and from 1.9 to 5.1 cm−3 number density. The volume density is well determined with 63.8–60.2 µm³/cm³ equivalent to about 2.5 ppmv of condensed water at 20 hPa. Simulations of lidar backscatter ratio based on these results are consistent with the lidar observations.

Nitric acid measurements at Eureka obtained in winter 2001–2002 using solar and lunar Fourier transform infrared absorption spectroscopy: Comparisons with observations at Thule and Kiruna and with results from three‐dimensional models

[1] For the first time, vertical column measurements of nitric acid (HNO3) above Eureka (80.1N, 86.4W), Canada, have been made during polar night using lunar spectra recorded with a Fourier transform infrared (FTIR) spectrometer, from October 2001 to March 2002. This site is part of the primary Arctic station of the Network for the Detection of Stratospheric Change. These measurements were compared with FTIR measurements at two other Arctic sites: Thule, Greenland (76.5N, 68.8W), and Kiruna, Sweden (67.8N, 20.4E). Eureka lunar measurements are in good agreement with solar ones made with the same instrument. Eureka and Thule HNO3 columns are consistent within measurement error. Differences between HNO3 columns at Kiruna and those at Eureka and Thule can be explained on the basis of available sunlight hours and location of the polar vortex. The measurements were also compared with results from a chemistry-climate model, the Canadian Middle Atmosphere Model (CMAM), and from a three-dimensional chemical transport model, SLIMCAT. This is the first time that CMAM HNO3 columns have been compared with observations in the Arctic. The comparison of CMAM HNO3 columns with Eureka and Kiruna data shows good agreement. The warm 2001–2002winterwithalmostnopolarstratosphericcloudsmakesthecomparisonwiththis version of CMAM, which has a known warm bias, a good test for CMAM under these conditions. SLIMCATcaptures the magnitude of HNO3 columns at Eureka, and the day-today variability, but generally reports higher values than were measured at Thule and Kiruna.

EFFECTS OF THE SELF-EMISSION OF AN IR FOURIER-TRANSFORM SPECTROMETER ON MEASURED ABSORPTION SPECTRA

Up to now the effect of the modulated thermal self-emission of Fourier-transform spectrometers has been investigated for emission measurements only. But this instrumental radiation also influences Fourier-transform absorption spectroscopy in the mid-IR when the Moon, a hot blackbody, or even the Sun is taken as a radiation source, e.g., by causing small negative radiance values in the center of saturated absorption lines. For our experimental investigations, a blackbody that can be cooled down to liquid-nitrogen temperature was constructed. Measurements at different temperatures of the blackbody and for different optical configurations in the detector port of the Fourier spectrometer as well as transmission measurements of gas cells are used to examine the statements above.

The exploitation of ground-based Fourier transform infrared observations for the evaluation of tropospheric trends of greenhouse gases over Europe

Abstract Solar absorption measurements using Fourier transform infrared (FTIR) spectrometry carry information about the atmospheric abundances of many constituents, including non-CO2 greenhouse gases. Such observations have regularly been made for many years as a contribution to the Network for the Detection of Stratospheric Change (NDSC). They are the only ground-based remote sensing observations available nowadays that carry information about a number of greenhouse gases in the free troposphere. This work focuses on the discussion of the information content of FTIR long-term monitoring data of some direct and indirect greenhouse gases (CH4, N2O, O3 and CO and C2H6, respectively), at six NDSC stations in Western Europe. This European FTIR network covers the polar to subtropical regions. At several stations of the network, the observations span more than a decade. Existing spectral time series have been reanalyzed according to a common optimized retrieval strategy, in order to derive distinct tropospheric and stratospheric abundances for the above-mentioned target gases. A bootstrap resampling method has been implemented to evaluate trends of the tropospheric burdens of the target gases, including their uncertainties. In parallel, simulations of the target time series are being made with the Oslo CTM2 model: comparisons between the model results and the observations provide valuable information to improve the model and, in particular, to optimize emission estimates that are used as inputs to the model simulations. The work is being performed within the EC project UFTIR. The paper focuses on N2O for which the first trend results have been obtained.