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The WPL (Webb, Pearman, and Leuning) correction is fully accepted to correct trace gas fluxes like CO2 for density fluctuations due to water vapour and temperature fluctuations for open-path gas analysers. It is known that this additive correction can be on the order of magnitude of the actual flux. However, this is hardly ever included in the analysis of data quality. An example from the Arctic shows the problems, because the size of the correction is a multiple of the actual flux. As a general result, we examined and tabulated the magnitude of the WPL correction for carbon dioxide flux as a function of sensible and latent heat flux. Furthermore, we propose a parameter to better estimate possible deficits in data quality and recommend integrating the quality flag derived with this parameter into the general study of small carbon dioxide fluxes.

Knowledge related to sulfur isotope ratios of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. An earlier method developed for sulfur isotopic analysis for OCS using S+ fragmentation by an isotope ratio mass spectrometer is inapplicable for ambient air samples because of the large samples required (approx. 500 L of 500 pmol mol−1 OCS). To overcome this difficulty, herein we present a new sampling system for collecting approximately 10 nmol of OCS from ambient air coupled with a purification system. Salient system features are (i) accommodation of samples up to 500 L (approx. 10 nmol) of air at 5 L min−1; (ii) portability of adsorption tubes (1∕4 in. (0.64 cm) outer diameter, 17.5 cm length, approximately 1.4 cm3 volume) for preserving the OCS amount and δ34S(OCS) values at −80 ∘C for up to 90 days and 14 days; and (iii) purification OCS from other compounds such as CO2. We tested the OCS collection efficiency of the systems and sulfur isotopic fractionation during sampling. Results show precision (1σ) of δ34S(OCS) values as 0.4 ‰ for overall procedures during measurements for atmospheric samples. Additionally, this report presents diurnal variation of δ34S(OCS) values collected from ambient air at the Suzukakedai campus of the Tokyo Institute of Technology located in Yokohama, Japan. The observed OCS concentrations and δ34S(OCS) values were, respectively, 447–520 pmol mol−1 and from 10.4 ‰ to 10.7 ‰ with a lack of diurnal variation. The observed δ34S(OCS) values in ambient air differed greatly from previously reported values of δ34S(OCS) = (4.9±0.3) ‰ for compressed air collected at Kawasaki, Japan, presumably because of degradation of OCS in cylinders and collection processes for that sample. The difference of atmospheric δ34S(OCS) values between 10.5 ‰ in Japan (this study) and ∼13 ‰ recently reported in Israel or the Canary Islands indicates that spatial and temporal variation of δ34S(OCS) values is expected due to a link between anthropogenic activities and OCS cycles. The system presented herein is useful for application of δ34S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle.

Experience of differential atmospheric absorption spectroscopy (DOAS) shows that a spectral shift between measurement spectra and reference spectra is frequently required in order to achieve optimal fit results, while the straightforward calculation of the optical density proves inferior. The shift is often attributed to temporal instabilities of the instrument but implicitly solved the problem of the tilt effect discussed/explained in this paper. Spectral positions of Fraunhofer and molecular absorption lines are systematically shifted for different measurement geometries due to an overall slope – or tilt – of the intensity spectrum. The phenomenon has become known as the tilt effect for limb satellite observations, where it is corrected for in a first-order approximation, whereas the remaining community is less aware of its cause and consequences. It is caused by the measurement process, because atmospheric absorption and convolution in the spectrometer do not commute. Highly resolved spectral structures in the spectrum will first be modified by absorption and scattering processes in the atmosphere before they are recorded with a spectrometer, which convolves them with a specific instrument function. In the DOAS spectral evaluation process, however, the polynomial (or other function used for this purpose) accounting for broadband absorption is applied after the convolution is performed. In this paper, we derive that changing the order of the two modifications of the spectra leads to different results. Assuming typical geometries for the observations of scattered sunlight and a spectral resolution of 0.6 nm, this effect can be interpreted as a spectral shift of up to 1.5 pm, which is confirmed in the actual analysis of the ground-based measurements of scattered sunlight as well as in numerical radiative transfer simulations. If no spectral shift is allowed by the fitting routine, residual structures of up to 2.5 × 10−3 peak-to-peak are observed. Thus, this effect needs to be considered for DOAS applications aiming at an rms of the residual of 10−3 and below.

In June 2009, 22 spectrometers from 14 institutes measured tropospheric and stratospheric NO2 from the ground for more than 11 days during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI), at Cabauw, NL (51.97° N, 4.93° E). All visible instruments used a common wavelength range and set of cross sections for the spectral analysis. Most of the instruments were of the multi-axis design with analysis by differential spectroscopy software (MAX-DOAS), whose non-zenith slant columns were compared by examining slopes of their least-squares straight line fits to mean values of a selection of instruments, after taking 30-min averages. Zenith slant columns near twilight were compared by fits to interpolated values of a reference instrument, then normalised by the mean of the slopes of the best instruments. For visible MAX-DOAS instruments, the means of the fitted slopes for NO2 and O4 of all except one instrument were within 10% of unity at almost all non-zenith elevations, and most were within 5%. Values for UV MAX-DOAS instruments were almost as good, being 12% and 7%, respectively. For visible instruments at zenith near twilight, the means of the fitted slopes of all instruments were within 5% of unity. This level of agreement is as good as that of previous intercomparisons, despite the site not being ideal for zenith twilight measurements. It bodes well for the future of measurements of tropospheric NO2, as previous intercomparisons were only for zenith instruments focussing on stratospheric NO2, with their longer heritage.

This paper investigates the scientific value of retrieving H218O and HDO columns in addition to H216O columns from high-resolution ground-based near-infrared spectra. We present a set of refined H216O, H218O, and HDO spectral windows. The retrieved H216O, H218O, and HDO columns are used for an a posteriori calculation of columnar δD and δ18O. We estimate the uncertainties for the so-calculated columnar δD and δ18O values. These estimations include uncertainties due to the measurement noise, errors in the a priori data, and uncertainties in spectroscopic parameters. Time series of δ18O obtained from ground-based FTIR (Fourier transform infrared) spectra are presented for the first time. For our study we use a full physics isotopic general circulation model (ECHAM5-wiso). We show that the full physics simulation of HDO and H218O can already be reasonably predicted from the H216O columns by a simple linear regression model (scatter values between full physics and linear regression simulations are 35 and 4‰ for HDO and H218O, respectively). We document that the columnar δD and δ18O values as calculated a posteriori from the retrievals of H216O, H218O, and HDO show a better agreement with the ECHAM5-wiso simulation than the δD and δ18O values as calculated from the H216O retrievals and the simple linear regression model. This suggests that the H218O and HDO column retrievals add complementary information to the H216O retrievals. However, these data have to be used carefully, because of the different vertical sensitivity of the H216O, H218O, and HDO columnar retrievals. Furthermore, we have to note that the retrievals use reanalysis humidity profiles as a priori input and the results are thus not independent of the reanalysis data.

In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2) from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS). In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used). A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

A new "Bayesian" minimization algorithm for the retrieval of the diurnal variation of UV/vis absorbing radicals (O3, NO2, BrO, OClO and HONO) from balloon-borne limb scattered skylight observations is discussed. The method evaluates spectroscopic measurements in combination with radiative transfer calculations to drive a mathematical inversion on a discrete time and height grid. Here, the proposed method is applied to data obtained during two deployments of the mini-DOAS instrument on different balloon payloads in northern Brazil in June 2005. The retrieval is tested by comparing the inferred profiles to in-situ ozone sounding data and to measurements of the ENVISAT/SCIAMACHY satellite instrument performed during a collocated overpass. The comparison demonstrates the strength and validity of our approach. In particular for time-varying radical concentrations, photochemical corrections due to temporal mismatch of the corresponding observations are rendered dispensable. Thus, limb scanning UV/vis spectrometry from balloon platforms offers a more direct and concise approach for satellite validation of radical measurements than solar occultation measurements. Furthermore, monitoring of the diurnal variation of stratospheric radicals allows us to constrain photochemical parameters which are critical for stratospheric ozone chemistry, such as the photolysis frequency of N2O5 by observations of the diurnal variation of NO2.