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Time series of total column abundances of hydrogen chloride (HCl), chlorine nitrate (ClONO2), and hydrogen fluoride (HF) were determined from ground-based Fourier transform infrared (FTIR) spectra recorded at 17 sites belonging to the Network for the Detection of Atmospheric Composition Change (NDACC) and located between 80.05° N and 77.82° S. By providing such a near-global overview on ground-based measurements of the two major stratospheric chlorine reservoir species, HCl and ClONO2, the present study is able to confirm the decrease of the atmospheric inorganic chlorine abundance during the last few years. This decrease is expected following the 1987 Montreal Protocol and its amendments and adjustments, where restrictions and a subsequent phase-out of the prominent anthropogenic chlorine source gases (solvents, chlorofluorocarbons) were agreed upon to enable a stabilisation and recovery of the stratospheric ozone layer. The atmospheric fluorine content is expected to be influenced by the Montreal Protocol, too, because most of the banned anthropogenic gases also represent important fluorine sources. But many of the substitutes to the banned gases also contain fluorine so that the HF total column abundance is expected to have continued to increase during the last few years. The measurements are compared with calculations from five different models: the two-dimensional Bremen model, the two chemistry-transport models KASIMA and SLIMCAT, and the two chemistry-climate models EMAC and SOCOL. Thereby, the ability of the models to reproduce the absolute total column amounts, the seasonal cycles, and the temporal evolution found in the FTIR measurements is investigated and inter-compared. This is especially interesting because the models have different architectures. The overall agreement between the measurements and models for the total column abundances and the seasonal cycles is good. Linear trends of HCl, ClONO2, and HF are calculated from both measurement and model t

We analyse the carbon monoxide (CO), ethane (C2H6) and hydrogen cyanide (HCN) partial columns (from the ground to 12 km) derived from measurements by ground-based solar Fourier Transform Spectroscopy at Lauder, New Zealand (45° S, 170° E), and at Arrival Heights, Antarctica (78° S, 167° E), from 1997 to 2009. Significant negative trends are calculated for all species at both locations, based on the daily-mean observed time series, namely CO (−0.94 ± 0.47% yr−1), C2H6 (−2.37 ± 1.18% yr−1) and HCN (−0.93 ± 0.47% yr−1) at Lauder and CO (−0.92 ± 0.46% yr−1), C2H6 (−2.82 ± 1.37% yr−1) and HCN (−1.41 ± 0.71% yr−1) at Arrival Heights. The uncertainties reflect the 95% confidence limits. However, the magnitudes of the trends are influenced by the anomaly associated with the 1997–1998 El Niño Southern Oscillation event at the beginning of the time series reported. We calculate trends for each month from 1997 to 2009 and find negative trends for all months. The largest monthly trends of CO and C2H6 at Lauder, and to a lesser degree at Arrival Heights, occur during austral spring during the Southern Hemisphere tropical and subtropical biomass burning period. For HCN, the largest monthly trends occur in July and August at Lauder and around November at Arrival Heights. The correlations between CO and C2H6 and between CO and HCN at Lauder in September to November, when the biomass burning maximizes, are significantly larger that those in other seasons. A tropospheric chemistry-climate model is used to simulate CO, C2H6, and HCN partial columns for the period of 1997–2009, using interannually varying biomass burning emissions from GFED3 and annually periodic but seasonally varying emissions from both biogenic and anthropogenic sources. The model-simulated partial columns of these species compare well with the measured partial columns and the model accurately reproduces seasonal cycles of all three species at both locations. However, while the model satisfactorily captures both the

The practical usefulness of a desktop optical spectrum analyzer (OSA) for measuring atmospheric CO2 and CH4 column densities at surface sites was examined in two separate measurement campaigns. The first comparison involved operating the OSA in parallel with a high resolution Fourier transform spectroscopy (FTS) situated at the University of Wollongong in Australia. Scale factors for the OSA were assigned for the column average volume mixing ratios of xCO2 and xCH4 by comparing with the well-studied FTS. The second method is a calibration against aircraft CO2 profiles in situ over Tsukuba in Japan obtained during a GOSAT validation campaign carried out from 28 January to 7 February 2011. The xCO2 values in the campaign, deduced by use of a derived OSA scale factor, were in excellent agreement with the integrated aircraft profiles.

We present a feasibility study into the use of solar remote sensing Fourier transform infrared spectrometry (FTS) to detect elusive trace gases in the marine boundary layer. The study acquired spectra from Wollongong, Australia (34.5°S, 150°E, 30m above sea level) at dawn as the sun rose over the ocean. We hoped to detect elusive atmospheric trace gases such as hypochlorous acid (HOCl) and dinitrogen pentoxide (N2O5) in these spectra, since the geometry results in path-lengths through the marine boundary layer in excess of 100km at dawn. Spectra were successfully collected at SZA greater than 90° above the marine horizon on four days due to the effects of diffraction in the atmosphere. Enhanced absorption features were observed for a large number of species and a spectral region for the possible observation of hypochlorous acid was identified. The experimental setup allowed for transmission of some infrared radiation but not enough to generate a sufficient signal to noise ratio for meaningful retrievals of total column amounts. Almost all absorption features were either saturated or had low signal to noise. Despite these problems, FTS has potential and some simple changes to the experimental setup could prove this to be a useful method.

The practical usefulness of a desktop optical spectrum analyzer (OSA) for measuring atmospheric CO2 and CH4 column densities at surface sites was examined in two separate measurement campaigns. The first comparison involved operating the OSA in parallel with a high resolution Fourier transform spectroscopy (FTS) situated at the University of Wollongong in Australia. Scale factors for the OSA were assigned for the column average volume mixing ratios of xCO2 and xCH4 by comparing with the well-studied FTS. The second method is a calibration against aircraft CO2 profiles in situ over Tsukuba in Japan obtained during a GOSAT validation campaign carried out from 28 January to 7 February 2011. The xCO2 values in the campaign, deduced by use of a derived OSA scale factor, were in excellent agreement with the integrated aircraft profiles.

This paper presents a validation study of SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) carbon monoxide (CO) total column measurements from the Iterative Maximum Likelihood Method (IMLM) algorithm using ground-based spectrometer observations from twenty surface stations for the five year time period of 2003–2007. Overall we find a good agreement between SCIAMACHY and ground-based observations for both mean values as well as seasonal variations. For high-latitude Northern Hemisphere stations absolute differences between SCIAMACHY and ground-based measurements are close to or fall within the SCIAMACHY CO 2 precision of 0.2×1018 molecules/cm2 (10%) indicating that SCIAMACHY can observe CO accurately at high Northern Hemisphere latitudes. For Northern Hemisphere mid-latitude stations the validation is complicated due to the vicinity of emission sources for almost all stations, leading to higher ground-based measurements compared to SCIAMACHY CO within its typical sampling area of 8 ×8. Comparisons with Northern Hemisphere mountain stations are hampered by elevation effects. After accounting for these effects, the validation provides satisfactory results

This paper presents extensive {bias determination} analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE) satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instrument. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from nearly 20 satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the average values of the mean relative differences are nearly all within +1 to +8%. At higher altitudes (4560 km), the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments, with mean relative differences of up to +40% (about +20% on average). For the ACE-MAESTRO version 1.2 ozone data product, mean relative differences are within ±10% (average values within ±6%) between 18 and 40 km for both the sunrise and sunset measurements. At higher altitudes (~3555 km), systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (with mean relative differences down to −10%), the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS, indicating a large positive bias (mean relative differences within +10 to +30%) in the 4555 km altitude range. In contrast, there is no significant systematic difference in bias found for the ACE-FTS sunrise and sunset measurements.

We report a 13-year (1992–2005) dataset of total column measurements of formaldehyde (HCHO) over Lauder, New Zealand, inferred from solar infrared spectra measured using a high-resolution Fourier Transform Spectrometer (FTS). Ambient HCHO concentrations at this rural location are often close to levels typical of remote marine environments (<250 ppt), which are close to the detection limit using standard techniques. Consequently we develop a new method that successfully produces HCHO columns with sufficient sensitivity throughout the whole season. HCHO columns over Lauder have a strong seasonal cycle (±50%), with a mean column of 4.9×1015 molecules cm−2, peaking during summer months. A simple box model of CH4 oxidation reproduces the observed broad-scale seasonal cycle, but significantly underestimates the seasonal peak HCHO ground concentrations during summer. This suggests the existence of an additional significant source of HCHO, possibly isoprene that cannot be explained by oxidation of CH4 alone. The ground-based FTS column data compare well with collocated HCHO column measurements from the Global Ozone Monitoring Experiment (GOME) satellite instrument during the operational period of GOME (1996–2001, r2=0.65, mean bias=10%, n=48).

We report the first atmospheric column measurements of methanol made by ground-based solar Fourier transform infrared spectroscopy. The measurements were made through smoke plumes over South Eastern Australia during the Austral summers of 2001/2002 and 2002/2003. There is a strong correlation between the measured column amounts of methanol and simultaneous and co-located measurements of aerosol optical depth. An emission factor for methanol from Australian forest fires of 2.3 ± 0.8 grams per kilogram of dry fuel consumed is estimated by use of the correlations of methanol and carbon monoxide with aerosol optical depth and literature values for the emission factor of carbon monoxide. This agrees well with literature values for emissions measured from extra-tropical forest fires elsewhere in the world. Methanol is clearly an important volatile organic product of forest fires with an emission factor similar to formaldehyde’s and approximately half that of methane.

We report the results of an intercomparison of vertical column amounts of hydrogen chloride (HCl), hydrogen fluoride (HF), nitrous oxide (N2O), nitric acid (HNO3), methane (CH4), ozone (O3), carbon dioxide (CO2) and nitrogen (N2) derived from the spectra recorded by two ground-based Fourier transform infrared (FTIR) spectrometers operated side-by-side using the sun as a source. The procedure used to record spectra and derive vertical column amounts follows the format of previous instrument intercomparisons organised by the Network for Detection of Atmospheric Composition Change (NDACC), formerly known as the Network for Detection of Stratospheric Change (NDSC). For most gases the differences were typically around 3% and in about half of the results the error bars given by the standard deviation of the measurements from each instrument did not overlap. The worst level of agreement was for HF where differences of over 5% were typical. The level of agreement achieved during this intercomparison is a little worse than that achieved in previous intercomparisons between ground-based FTIR spectrometers.

The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), on-board the European ENVIronmental SATellite (ENVISAT) launched on 1 March 2002, is a middle infrared Fourier Transform spectrometer measuring the atmospheric emission spectrum in limb sounding geometry. The instrument is capable to retrieve the vertical distribution of temperature and trace gases, aiming at the study of climate and atmospheric chemistry and dynamics, and at applications to data assimilation and weather forecasting.