Hydrogen fluoride total and partial column time series above the Jungfraujoch from long-term FTIR measurements: Impact of the line-shape model, characterization of the error budget and seasonal cycle, and comparison with satellite and model data

in Journal of Geophysical Research. Atmospheres (2010), 115

Time series of hydrogen fluoride (HF) total columns have been derived from ground-based Fourier transform infrared (FTIR) solar spectra recorded between March 1984 and December 2009 at the International ... [more ▼]

Time series of hydrogen fluoride (HF) total columns have been derived from ground-based Fourier transform infrared (FTIR) solar spectra recorded between March 1984 and December 2009 at the International Scientific Station of the Jungfraujoch (Swiss Alps, 46.5°N, 8.0°E, 3580 m asl) with two high resolution spectrometers (one home-made and one Bruker 120-HR). Solar spectra have been inverted with the PROFFIT 9.5 algorithm, using the optimal estimation method. An inter-comparison of HF total columns retrieved with PROFFIT and SFIT-2 – the other reference algorithm in the FTIR community - is performed for the first time. The effect of a Galatry line shape model on HF retrieved total columns and vertical profiles, on the residuals of the fits and on the error budget is also quantified. Information content analysis indicates that, in addition to HF total vertical abundance, three independent stratospheric HF partial columns can be derived from our Bruker spectra. A complete error budget has been established and indicates that the main source of systematic error is linked to HF spectroscopy and that the random error affecting our HF total columns does not exceed 2.5%. Ground-based middle and upper stratospheric HF amounts have been compared to satellite data collected by the HALOE or ACE-FTS instruments. Comparisons of our FTIR HF total and partial columns with runs performed by two 3D numerical models (SLIMCAT and KASIMA) are also included. Finally, FTIR and model HF total and partial columns time series have been analyzed to derive the main characteristics of their seasonal cycles. [less ▲]

Free tropospheric measurements of formic acid (HCOOH) from infrared ground-based solar absorption spectra: Retrieval approach, evidence for a seasonal cycle, and comparison with model calculations

in Journal of Geophysical Research. Atmospheres (2004), 109(D18),

The seasonal variation of the free tropospheric volume mixing ratio of formic acid (HCOOH) has been derived from high-spectral-resolution solar absorption spectra recorded with the Fourier transform ... [more ▼]

The seasonal variation of the free tropospheric volume mixing ratio of formic acid (HCOOH) has been derived from high-spectral-resolution solar absorption spectra recorded with the Fourier transform spectrometer in the U. S. National Solar Observatory facility on Kitt Peak (31.9degreesN, 111.6degreesE, 2.09 km altitude) at a typical spectral resolution of 0.005 cm(-1). The spectra have been analyzed with the SFIT2 algorithm, which is based on a semiempirical application of the optimal estimation method. Absorption by HCOOH is weak in these solar spectra, but successful retrievals have been obtained with a new procedure that fits the HCOOH nu(6) band Q branch at 1105 cm(-1) simultaneously with a window to account for a temperature-sensitive HDO line, which overlaps the HCOOH Q branch. After retaining only the best measurements from a database extending from June 1980 to October 2002 the retrievals show a seasonal variation, with a summer maximum and a winter minimum. Average 2.09-10 km volume mixing ratios binned in 3 month intervals range from a maximum of 792+/-323 parts per trillion by volume (pptv), or 10(-12), in July-September to a minimum of 313+/-175 pptv in October-December, with the uncertainties corresponding to statistical means from daily averages. The results are compared with previously reported measurements and model calculations. [less ▲]

Post-Mount Pinatubo eruption ground-based infrared stratospheric column measurements of HNO3, NO, and NO2 and their comparison with model calculations

in Journal of Geophysical Research. Atmospheres (2003), 108(D15),

[1] Infrared solar spectra recorded between July 1991 to March 1992 and November 2002 with the Fourier transform spectrometer on Kitt Peak (31.9 degrees N latitude, 111.6 degrees W longitude, 2.09 km ... [more ▼]

[1] Infrared solar spectra recorded between July 1991 to March 1992 and November 2002 with the Fourier transform spectrometer on Kitt Peak (31.9 degrees N latitude, 111.6 degrees W longitude, 2.09 km altitude) have been analyzed to retrieve stratospheric columns of HNO3, NO, and NO2. The measurements cover a decade time span following the June 1991 Mount Pinatubo volcanic eruption and were recorded typically at 0.01 cm(-1) spectral resolution. The measured HNO3 stratospheric column shows a 20% decline from 9.16 x 10(15) molecules cm(-2) from the first observation in March 1992 to 7.40 x 10(15) molecules cm(-2) at the start of 1996 reaching a broad minimum of 6.95 x 10(15) molecules cm(-2) thereafter. Normalized daytime NO and NO2 stratospheric column trends for the full post-Pinatubo eruption time period equal (+ 1.56 +/- 0.45)% yr(-1), 1 sigma, and (+ 0.52 +/- 0.32)% yr(-1), 1 sigma, respectively. The long-term trends are superimposed on seasonal cycles with ~10% relative amplitudes with respect to mean values, winter maxima for HNO3 and summer maxima for NO and NO2. The measurements have been compared with two-dimensional model calculations utilizing version 6.1 Stratospheric Aerosol and Gas Experiment ( SAGE) II sulfate aerosol surface area density measurements through 1999 and extended to the end of the time series by repeating the 1999 values. The model-calculated HNO3, NO, and NO2 stratospheric column time series agree with the measurements to within ~8% after taking into account the vertical sensitivity of the ground-based measurements. The consistency between the measured and model-calculated stratospheric time series confirms the decreased impact on stratospheric reactive nitrogen chemistry of the key heterogeneous reaction that converts reactive nitrogen to its less active reservoir form as the lower-stratospheric aerosol surface area density declined by a factor of ~20 after the eruption maximum. [less ▲]

Statistical derivation of the evolution equation of liquid water path fluctuations in clouds

in Journal of Geophysical Research. Atmospheres (2002), 107(D23),

[1] How to distinguish and quantify deterministic and random influences on the statistics of turbulence data in meteorology cases is discussed from first principles. Liquid water path (LWP) changes in ... [more ▼]

[1] How to distinguish and quantify deterministic and random influences on the statistics of turbulence data in meteorology cases is discussed from first principles. Liquid water path (LWP) changes in clouds, as retrieved from radio signals, upon different delay times, can be regarded as a stochastic Markov process. A detrended fluctuation analysis method indicates the existence of long range time correlations. The Fokker-Planck equation which models very precisely the LWP fluctuation empirical probability distributions, in particular, their non-Gaussian heavy tails is explicitly derived and written in terms of a drift and a diffusion coefficient. Furthermore, Kramers-Moyal coefficients, as estimated from the empirical data, are found to be in good agreement with their first principle derivation. Finally, the equivalent Langevin equation is written for the LWP increments themselves. Thus rather than the existence of hierarchical structures, like an energy cascade process, strong correlations on different timescales, from small to large ones, are considered to be proven as intrinsic ingredients of such cloud evolutions. [less ▲]

Multiyear infrared solar spectroscopic measurements of HCN, CO, C2H6,and C2H2 tropospheric columns above Lauder, New Zealand (45 degrees S latitude)

in Journal of Geophysical Research. Atmospheres (2002), 107(D14),

[1] Near-simultaneous, 0.0035 or 0.007 cm(-1) resolution infrared solar absorption spectra of tropospheric HCN, C2H2, CO, and C2H6 have been recorded from the Network for the Detection of Stratospheric ... [more ▼]

[1] Near-simultaneous, 0.0035 or 0.007 cm(-1) resolution infrared solar absorption spectra of tropospheric HCN, C2H2, CO, and C2H6 have been recorded from the Network for the Detection of Stratospheric Change station in Lauder, New Zealand (45.04degreesS, 169.68degreesE, 0.37 km altitude). All four molecules were measured on over 350 days with HCN and C2H2 reported for the first time based on a new analysis procedure that significantly increases the effective signal-to-noise of weak tropospheric absorption features in the measured spectra. The CO measurements extend by 2.5 years a database of measurements begun in January 1994 for CO with improved sensitivity in the lower and middle troposphere. The C2H6 measurements lengthen a time series begun in July 1993 with peak sensitivity in the upper troposphere. Retrievals of all four molecules were obtained with an algorithm based on the semiempirical application of the Rodgers optimal estimation technique. Columns are reported for the 0.37- to 12-km-altitude region, approximately the troposphere above the station. The seasonal cycles of all four molecules are asymmetric, with minima in March-June and sharp peaks and increased variability during August-November, which corresponds to the period of maximum biomass burning near the end of the Southern Hemisphere tropical dry season. Except for a possible HCN column decrease, no evidence was found for a statistically significant long-term trend. [less ▲]

Free tropospheric CO, C2H6, and HCN above central Europe: Recent measurements from the Jungfraujoch station including the detection of elevated columns during 1998

in Journal of Geophysical Research. Atmospheres (2000), 105(D19), 24235-24249

Time series of free tropospheric carbon monoxide (CO), ethane (C2H6), and hydrogen cyanide (HCN) column abundances have been derived from observations at the International Scientific Station of the ... [more ▼]

Time series of free tropospheric carbon monoxide (CO), ethane (C2H6), and hydrogen cyanide (HCN) column abundances have been derived from observations at the International Scientific Station of the Jungfraujoch (ISSJ) at 3.58-km altitude in the Swiss Alps (latitude 46.55 degreesN, 7.98 degreesE longitude). The free troposphere was assumed to extend from 3.58 to 11 km altitude, and the related columns were derived for all three molecules from high spectral resolution infrared solar spectra recorded between January 1995 and October 1999. The three molecules show distinct seasonal cycles with maxima during winter for CO and C2H6, and during spring for HCN. These seasonal changes are superimposed on interannual variations. The tropospheric columns of all three molecules were elevated during 1998. Increases were most pronounced for HCN with enhanced values throughout the year, up to a factor of 2 in January 1998 when compared to averages of the other years. The increased tropospheric columns coincide with the period of widespread wildfires during the strong El Nino warm phase of 1997-1998. The emission enhancements above ISSJ are less pronounced, and they peaked after the increases measured above Mauna Loa (19.55 degreesN, 155.6 degreesW). Tropospheric trends for CO, C2H6, and HCN of (2.40 +/- 0.49), (0.47 +/- 0.64), and (7.00 +/- 1.61)% yr(-1)(1 sigma) were derived for January 1995 to October 1999. However, if 1998 measurements are excluded from the fit, CO and HCN trends that are not statistically significant, and a statistically significant decrease in the C2H6 tropospheric column, are inferred. Comparisons of the infrared CO columns with CO in situ surface measurements suggest that the CO free tropospheric vertical Volume mixing ratio profile generally decreases with altitude throughout the year. [less ▲]

Polar stratospheric descent of NOy and CO and Arctic denitrification during winter 1992-1993

in Journal Of Geophysical Research. Atmospheres (1999), 104(D1), 1847-1861

Observations inside the November 1994 Antarctic stratospheric vortex and inside the April 1993 remnant Arctic stratospheric vortex by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform ... [more ▼]

Observations inside the November 1994 Antarctic stratospheric vortex and inside the April 1993 remnant Arctic stratospheric vortex by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer are reported. In both instances, elevated volume mixing ratios (VMRs) of carbon monoxide (CO) were measured. A peak Antarctic CO VMR of 60 ppbv (where 1 ppbv = 10(-9) per unit volume) was measured at a potential temperature (Theta) of 710 K (similar to 27 km), about 1 km below the altitude of a pocket of elevated NOy (total reactive nitrogen) at a deep minimum in N2O (<5 ppbv). The Arctic observations also show a region of elevated vortex CO with a peak VMR of 90 ppbv at 630-670 K (similar to 25 km) but no corresponding enhancement in NOy, perhaps because of stronger dynamical activity in the northern hemisphere polar winter and/or interannual variability in the production of mesospheric NO. By comparing vortex and extravortex observations of NOy obtained at the same N2O VMR, Arctic vortex denitrification of 5 +/- 2 ppbv at 470 K (similar to 18 km) is inferred. We show that our conclusion of substantial Arctic winter 1992-1993 denitrification is robust by comparing our extravortex observations with previous polar measurements obtained over a wide range of winter conditions. Correlations of NOy with N2O measured at the same Theta by ATMOS in the Arctic vortex and at midlatitudes on board the ER-2 aircraft several weeks later lie along the same mixing line. The result demonstrates the consistency of the two data sets and confirms that the ER-2 sampled fragments of the denitrified Arctic vortex following its breakup, An analysis of the ATMOS Arctic measurements of total hydrogen shows no evidence for significant dehydration inside the vortex. [less ▲]

Northern and southern hemisphere ground-based infrared spectroscopic measurements of tropospheric carbon monoxide and ethane

in Journal Of Geophysical Research. Atmospheres (1998), 103(D21), 28197-28217

Time series of CO and C2H6 measurements have been derived from high-resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 degrees S, 169.7 degrees E, altitude 0.37 km), and at the U.S ... [more ▼]

Time series of CO and C2H6 measurements have been derived from high-resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 degrees S, 169.7 degrees E, altitude 0.37 km), and at the U.S. National Solar Observatory (31.9 degrees N, 111.6 degrees W, altitude 2.09 km) on Kitt Peak. Lauder observations were obtained between July 1993 and November 1997, while the Kitt Peak measurements were recorded between May 1977 and December 1997. Both databases were analyzed with spectroscopic parameters that included significant improvements for C2H6 relative to previous studies. Target CO and C2H6 lines were selected to achieve similar vertical samplings based on averaging kernels. These calculations show that partial columns from layers extending from the surface to the mean tropopause and from the mean tropopause to 100 km are nearly independent. Retrievals based on a semiempirical application of the Rodgers optimal estimation technique are reported for the lower laver, which has a broad maximum in sensitivity in the upper troposphere. The Lauder CO and C2H6 partial columns exhibit highly asymmetrical seasonal cycles with minima in austral autumn and sharp peaks in austral spring. The spring maxima are the result of tropical biomass burning emissions followed by deep convective vertical transport to the upper troposphere and long-range horizontal transport. Significant year-to-year variations are observed for both CO and C2H6, but the measured trends, (+0.37 +/- 0.57)% yr(-1) and (-0.64 +/- 0.79)% yr(-1), 1 sigma, respectively, indicate no significant long-term changes. The Kitt Peak data also exhibit CO and C2H6 seasonal variations in the lower layer with trends equal to (-0.27 +/- 0.17)% yr(-1) and (-1.20 +/- 0.35')% yr(-1), 1 sigma, respectively. Hence a decrease in the Kitt Peak tropospheric C2H6 column has been detected, though the CO trend is not significant. Both measurement sets are compared with previous observations, reported trends, and three-dimensional model calculations. [less ▲]