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Relying on high resolution Fourier transform infrared (FIR) spectra the present work involved extensive measurements of individual line intensities and self broadening coefficients for the nu(7) band of (C2H4) C 12. The measured self broadening coefficients exhibit a dependence on both J and K a. Compared to the corresponding information available in the latest edition of the HITRAN spectroscopic database the measured line intensities were found to be higher by about 10 for high] lines in the P branch and lower by about 5 for high J lines of the R branch varying between these two limits roughly linearly with the line positions. The impact of the presently measured line intensities on retrievals of atmospheric ethylene in the 949.0 952.0 cm( 1) microwindow was evaluated using a subset of ground based high resolution FTIR solar spectra recorded at the Jungfraujoch station. The use of HITRAN 2012 with line intensities modified to match the present measurements led to a systematic reduction of the measured total columns of ethylene by 4.1 +/ 0.1. (C) 2014 Elsevier Ltd. All rights reserved.

The long-term evolution of the vertical column abundance of carbon tetrafluoride (CF4) above the high-altitude Jungfraujoch station (Swiss Alps, 46.5° N, 8.0° E, 3580 m a.s.l.) has been derived from the spectrometric analysis of Fourier transform infrared solar spectra recorded at that site between 1989 and 2012. The investigation is based on a multi-microwindow approach, two encompassing pairs of absorption lines belonging to the R-branch of the strong ν3 band of CF4 centered at 1283 cm−1, and two additional ones to optimally account for weak but overlapping HNO3 interferences. The analysis reveals a steady accumulation of the very long-lived CF4 above the Jungfraujoch at mean rates of (1.38 ± 0.11) × 1013 molec cm−2 yr−1 from 1989 to 1997, and (0.98 ± 0.02) × 1013 molec cm−2 yr−1 from 1998 to 2012, which correspond to linear growth rates of 1.71 ± 0.14 and 1.04 ± 0.02% yr−1 respectively referenced to 1989 and 1998. Related global CF4 anthropogenic emissions required to sustain these mean increases correspond to 15.8 ± 1.3 and 11.1 ± 0.2 Gg yr−1 over the above specified time intervals. Findings reported here are compared and discussed with respect to relevant northern mid-latitude results obtained remotely from space and balloons as well as in situ at the ground, including new gas chromatography mass spectrometry measurements performed at the Jungfraujoch since 2010.

Interest in stratospheric aerosol and its role in climate have increased over the last decade due to the observed increase in stratospheric aerosol since 2000 and the potential for changes in the sulfur cycle induced by climate change. This review provides an overview about the advances in stratospheric aerosol research since the last comprehensive assessment of stratospheric aerosol was published in 2006. A crucial development since 2006 is the substantial improvement in the agreement between in situ and space-based inferences of stratospheric aerosol properties during volcanically quiescent periods. Furthermore, new measurement systems and techniques, both in situ and space based, have been developed for measuring physical aerosol properties with greater accuracy and for characterizing aerosol composition. However, these changes induce challenges to constructing a long-term stratospheric aerosol climatology. Currently, changes in stratospheric aerosol levels less than 20% cannot be confidently quantified. The volcanic signals tend to mask any nonvolcanically driven change, making them difficult to understand. While the role of carbonyl sulfide as a substantial and relatively constant source of stratospheric sulfur has been confirmed by new observations and model simulations, large uncertainties remain with respect to the contribution from anthropogenic sulfur dioxide emissions. New evidence has been provided that stratospheric aerosol can also contain small amounts of nonsulfate matter such as black carbon and organics. Chemistry-climate models have substantially increased in quantity and sophistication. In many models the implementation of stratospheric aerosol processes is coupled to radiation and/or stratospheric chemistry modules to account for relevant feedback processes.

The trend in stratospheric NO2 column at the NDACC (Network for the Detection of Atmospheric Composition Change) station of Jungfraujoch (46.5° N, 8.0° E) is assessed using ground-based FTIR and zenith-scattered visible sunlight SAOZ measurements over the period 1990 to 2009 as well as a composite satellite nadir data set constructed from ERS-2/GOME, ENVISAT/SCIAMACHY, and METOP-A/GOME-2 observations over the 1996–2009 period. To calculate the trends, a linear least squares regression model including explanatory variables for a linear trend, the mean annual cycle, the quasi-biennial oscillation (QBO), solar activity, and stratospheric aerosol loading is used. For the 1990–2009 period, statistically indistinguishable trends of −3.7 ± 1.1% decade−1 and −3.6 ± 0.9% decade−1 are derived for the SAOZ and FTIR NO2 column time series, respectively. SAOZ, FTIR, and satellite nadir data sets show a similar decrease over the 1996–2009 period, with trends of −2.4 ± 1.1% decade−1, −4.3 ± 1.4% decade−1, and −3.6 ± 2.2% decade−1, respectively. The fact that these declines are opposite in sign to the globally observed +2.5% decade−1 trend in N2O, suggests that factors other than N2O are driving the evolution of stratospheric NO2 at northern mid-latitudes. Possible causes of the decrease in stratospheric NO2 columns have been investigated. The most likely cause is a change in the NO2/NO partitioning in favor of NO, due to a possible stratospheric cooling and a decrease in stratospheric chlorine content, the latter being further confirmed by the negative trend in the ClONO2 column derived from FTIR observations at Jungfraujoch. Decreasing ClO concentrations slows the NO + ClO → NO2 + Cl reaction and a stratospheric cooling slows the NO + O3 → NO2 + O2 reaction, leaving more NOx in the form of NO. The slightly positive trends in ozone estimated from ground- and satellite-based data sets are also consistent with the decrease of NO2 through the NO2 + O3 → NO3 + O2 reaction. Finally, we cannot rule out the possibility that a strengthening of the Dobson-Brewer circulation, which reduces the time available for N2O photolysis in the stratosphere, could also contribute to the observed decline in stratospheric NO2 above Jungfraujoch.

Measurements of the atmospheric HDO/H$_{2}$O ratio help us to better understand the hydrological cycle and improve models to correctly simulate tropospheric humidity and therefore climate change. We present an updated version of the column-averaged HDO/H$_{2}$O ratio data set from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The data set is extended with 2 additional years, now covering 2003–2007, and is validated against co-located ground-based total column δD measurements from Fourier transform spectrometers (FTS) of the Total Carbon Column Observing Network (TCCON) and the Network for the Detection of Atmospheric Composition Change (NDACC, produced within the framework of the MUSICA project). Even though the time overlap among the available data is not yet ideal, we determined a mean negative bias in SCIAMACHY δD of -35±30‰ compared to TCCON and -69±15‰ compared to MUSICA (the uncertainty indicating the station-to-station standard deviation). The bias shows a latitudinal dependency, being largest (~-60 to -80 ‰) at the highest latitudes and smallest (~-20 to -30 ‰) at the lowest latitudes. We have tested the impact of an offset correction to the SCIAMACHY HDO and H$_{2}$O columns. This correction leads to a humidity- and latitude-dependent shift in δD and an improvement of the bias by 27 ‰, although it does not lead to an improved correlation with the FTS measurements nor to a strong reduction of the latitudinal dependency of the bias. The correction might be an improvement for dry, high-altitude areas, such as the Tibetan Plateau and the Andes region. For these areas, however, validation is currently impossible due to a lack of ground stations. The mean standard deviation of single-sounding SCIAMACHY–FTS differences is ~115 ‰, which is reduced by a factor ~2 when we consider monthly means. When we relax the strict matching of individual measurements and focus on the mean seasonalities using all available FTS data, we find that the correlation coefficients between SCIAMACHY and the FTS networks improve from 0.2 to 0.7–0.8. Certain ground stations show a clear asymmetry in δD during the transition from the dry to the wet season and back, which is also detected by SCIAMACHY. This asymmetry points to a transition in the source region temperature or location of the water vapour and shows the added information that HDO/H$_{2}$O measurements provide when used in combination with variations in humidity.

Within the NDACC (Network for the Detection of Atmospheric Composition Change), more than 20 FTIR (Fourier-transform infrared) spectrometers, spread worldwide, provide long-term data records of many atmospheric trace gases. We present a method that uses measured and modelled XCO2 for assessing the consistency of these NDACC data records. Our XCO2 retrieval setup is kept simple so that it can easily be adopted for any NDACC/FTIR-like measurement made since the late 1950s. By a comparison to coincident TCCON (Total Carbon Column Observing Network) measurements, we empirically demonstrate the useful quality of this suggested NDACC XCO2 product (empirically obtained scatter between TCCON and NDACC is about 4‰ for daily mean as well as monthly mean comparisons, and the bias is 25‰). Our XCO2 model is a simple regression model fitted to CarbonTracker results and the Mauna Loa CO2 in situ records. A comparison to TCCON data suggests an uncertainty of the model for monthly mean data of below 3‰. We apply the method to the NDACC/FTIR spectra that are used within the project MUSICA (multi-platform remote sensing of isotopologues for investigating the cycle of atmospheric water) and demonstrate that there is a good consistency for these globally representative set of spectra measured since 1996: the scatter between the modelled and measured XCO2 on a yearly time scale is only 3‰.

Hydrogen cyanide (HCN) and acetylene (C2H2) are ubiquitous atmospheric trace gases with medium lifetime, which are frequently used as indicators of combustion sources and as tracers for atmospheric transport and chemistry. Because of their weak infrared absorption, overlapped by the CO2 Q branch near 720 cm-1, nadir sounders have up to now failed to measure these gases routinely. Taking into account CO 2 line mixing, we provide for the first time extensive measurements of HCN and C2H2 total columns at Reunion Island (21° S, 55° E) and Jungfraujoch (46° N, 8° E) in 2009-2010 using observations from the Infrared Atmospheric Sounding Interferometer (IASI). A first order comparison with local ground-based Fourier transform infraRed (FTIR) measurements has been carried out allowing tests of seasonal consistency which is reasonably captured, except for HCN at Jungfraujoch. The IASI data shows a greater tendency to high C2H2 values. We also examine a nonspecific biomass burning plume over austral Africa and show that the emission ratios with respect to CO agree with previously reported values. © Author(s) 2013., SCOPUS: ar.j, info:eu-repo/semantics/published

Trends in the CO and C2H6 partial columns (~0–15 km) have been estimated from four European groundbasedsolar FTIR (Fourier Transform InfraRed) stations for the 1996–2006 time period. The CO trends from the four stations Jungfraujoch, Zugspitze, Harestua and Kiruna have been estimated to −0.45±0.16%yr−1, −1.00 ± 0.24%yr−1, −0.62±0.19%yr−1 and −0.61±0.16%yr−1, respectively. The corresponding trends for C2H6 are−1.51±0.23%yr−1, −2.11±0.30%yr−1, −1.09±0.25%yr−1 and −1.14±0.18%yr−1. All trends are presented with their 2-σ confidence intervals. To find possible reasons for the CO trends, the global-scale EMEP MSC-W chemical transport model has been used in a series of sensitivity scenarios. It is shown that the trends are consistent with the combination of a 20% decrease in the anthropogenic CO emissions seen in Europe and North America during the 1996–2006 period and a 20% increase in the anthropogenic CO emissions in East Asia, during the same time period. The possible impacts of CH4 and biogenic volatile organic compounds (BVOCs) are also considered. The European and global-scale EMEP models have been evaluated against the measured CO and C2H6 partial columns from Jungfraujoch, Zugspitze, Bremen, Harestua, Kiruna and Ny-Ålesund. The European model reproduces, on average the measurements at the different sites fairly well and within 10–22% deviation for CO and 14–31% deviation for C2H6. Their seasonal amplitude is captured within 6–35% and 9–124% for CO and C2H6, respectively. However, 61–98% of the CO and C2H6 partial columns in the European model are shown to arise from the boundary conditions, making the globalscale model a more suitable alternative when modeling these two species. In the evaluation of the global model the average partial columns for 2006 are shown to be within 1–9% and 37–50% of the measurements for CO and C2H6, respectively. The global model sensitivity for assumptions made in this paper is also analyzed.

Total columns measured with the ground-based solar FTIR technique are highly variable in time due to atmospheric chemistry and dynamics in the atmosphere above the measurement station. In this paper, a multiple regression model with anomalies of air pressure, total columns of hydrogen fluoride (HF) and carbon monoxide (CO) and tropopause height are used to reduce the variability in the methane (CH4) and nitrous oxide (N2O) total columns to estimate reliable linear trends with as small uncertainties as possible. The method is developed at the Harestua station (60°N, 11°E, 600ma.s.l.) and used on three other European FTIR stations, i.e. Jungfraujoch (47°N, 8°E, 3600ma.s.l.), Zugspitze (47°N, 11°E, 3000ma.s.l.), and Kiruna (68°N, 20°E, 400ma.s.l.). Linear CH4 trends between 0.13±0.01-0.25±0.02%yr−1 were estimated for all stations in the 1996-2009 period. A piecewise model with three separate linear trends, connected at change points, was used to estimate the short term fluctuations in the CH4 total columns. This model shows a growth in 1996–1999 followed by a period of steady state until 2007. From 2007 until 2009 the atmospheric CH4 amount increases between 0.57±0.22–1.15±0.17%yr−1. Linear N2O trends between 0.19±0.01–0.40±0.02%yr−1 were estimated for all stations in the 1996-2007 period, here with the strongest trend at Harestua and Kiruna and the lowest at the Alp stations. From the N2O total columns crude tropospheric and stratospheric partial columns were derived, indicating that the observed difference in the N2O trends between the FTIR sites is of stratospheric origin. This agrees well with the N2O measurements by the SMR instrument onboard the Odin satellite showing the highest trends at Harestua, 0.98±0.28%yr−1, and considerably smaller trends at lower latitudes, 0.27±0.25%yr−1. The multiple regression model was compared with two other trend methods, the ordinary linear regression and a Bootstrap algorithm. The multiple regression model estimated CH4 and N2O trends that differed up to 31% compared to the other two methods and had uncertainties that were up to 300% lower. Since the multiple regression method were carefully validated this stresses the importance to account for variability in the total columns when estimating trend from solar FTIR data.

We present an original multi-spectrum fitting procedure to retrieve volume mixing ratio (VMR) profiles of carbonyl fluoride (COF2) from ground-based high resolution Fourier transform infrared (FTIR) solar spectra. The multi-spectrum approach consists of simultaneously combining, during the retrievals, all spectra recorded consecutively during the same day and with the same resolution. Solar observations analyzed in this study with the SFIT-2 v3.91 fitting algorithm correspond to more than 2900 spectra recorded between January 2000 and December 2007 at high zenith angles, with a Fourier Transform Spectrometer operated at the high-altitude International Scientific Station of the Jungfraujoch (ISSJ, 46.5° N latitude, 8.0° E longitude, 3580m altitude), Switzerland. The goal of the retrieval strategy described here is to provide information about the vertical distribution of carbonyl fluoride. The microwindows used are located in the υ1 or in the υ4 COF2 infrared (IR) absorption bands. Averaging kernel and eigenvector analysis indicates that our FTIR retrieval is sensitive to COF2 inversion between 17 and 30 km, with the major contribution to the retrieved information always coming from the measurement. Moreover, there was no significant bias between COF2 partial columns, total columns or VMR profiles retrieved from the two bands. For each wavenumber region, a complete error budget including all identified sources has been carefully established. In addition, comparisons of FTIR COF2 17–30 km partial columns with KASIMA and SLIMCAT 3-D CTMs are also presented. If we do not notice any significant bias between FTIR and SLIMCAT time series, KASIMA COF2 17–30 km partial columns are lower of around 25%, probably due to incorrect lower boundary conditions. For each times series, linear trend estimation for the 2000–2007 time period as well as a seasonal variation study are also performed and critically discussed. For FTIR and KASIMA time series, very low COF2 growth rates (0.4±0.2%/year and 0.3±0.2%/year, respectively) have been derived. However, the SLIMCAT data set gives a slight negative trend (−0.5±0.2%/year), probably ascribable to discontinuities in the meteorological data used by this model. We further demonstrate that all time series are able to reproduce the COF2 seasonal cycle, which main seasonal characteristics deduced from each data set agree quite well.

The ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) solar occultation instrument that was launched onboard the Canadian SCISAT-1 satellite in August 2003 is measuring vertical profiles from the upper troposphere to the lower mesosphere for a large number of atmospheric constituents. Methane is one of the key species. The version v2.2 data of the ACE-FTS CH4 data have been compared to correlative satellite, balloon-borne and ground-based Fourier transform infrared remote sensing data to assess their quality. The comparison results indicate that the accuracy of the data is within 10% in the upper troposphere – lower stratosphere, and within 25% in the middle and higher stratosphere up to the lower mesosphere (