Improved calibration procedures for the EM27/SUN spectrometers of the COllaborative Carbon Column Observing Network (COCCON)

In this study, an extension on the previously reported status of the COllaborative Carbon Column Observing Network’s (COCCON) calibration procedures incorporating refined methods is presented. COCCON is a global network of portable Bruker EM27/SUN FTIR spectrometers for deriving column-averaged atmospheric abundances of greenhouse gases. The original laboratory open-path lamp measurements for deriving the instrumental line shape (ILS) of the spectrometer from water vapour lines have been refined and extended to the secondary detector channel incorporated in the EM27/SUN spectrometer for detection of carbon monoxide (CO). The refinements encompass improved spectroscopic line lists for the relevant water lines and a revision of the laboratory pressure measurements used for the analysis of the spectra. The new results are found to be in good agreement with those reported by Frey et al. (2019), and discussed in detail. In addition, a new calibration cell for ILS measurements was designed, constructed and put into service. Spectrometers calibrated since January 2020 were tested using both methods for ILS characterisation, open path (OP) and cell measurements. We demonstrate that both methods can detect the small variations of ILS characteristics between different spectrometers, but the results of the cell method indicate a systematic bias of the OP method. Finally, a revision and extension of the COCCON network instrument-to-instrument calibration factors for XCO2, XCO, and XCH4 is presented, incorporating 47 new spectrometers (of 83 in total by now). This calibration is based on the reference EM27/SUN spectrometer operated by the Karlsruhe Institute of Technology (KIT) and spectra collected by the collocated TCCON station Karlsruhe. Variations in the instrumental characteristics of the reference EM27/SUN during 2014 to 2017 were detected probably arising from realignment and the dual-channel upgrade performed in early 2018. These variations are considered in the evaluation of the instrument-specific calibration factors in order to keep all tabulated calibration results consistent.

High resolution ro–vibrational analysis of molecules in doublet electronic states: the ν1 fundamental of chlorine dioxide (16O35Cl16O) in the X2B1 electronic ground state

We report the spectrum of the ν1 fundamental of ClO2 centered in the infrared atmospheric window at 945.592 cm−1 measured with essentially Doppler limited resolution at an instrumental line width of 0.001 cm−1 using the Zürich prototype ZP2001 FTIR spectrometer.

The Influence of Instrumental Line Shape Degradation on the Partial Columns of O3, CO,CH4 and N2O Derived from High-Resolution FTIR spectrometry

High resolution Fourier transform infrared (FTIR) measurement of direct sunlight does not only provide information of trace gas total columns, but also vertical distribution. Measured O3, CO, CH4, and N2O can be separated into multiple partial columns using the optimal estimation method (OEM). The retrieval of trace gas profiles is sensitive to the instrument line shape (ILS) of the FTIR spectrometer. In this paper, we present an investigation of the influence of ILS degradation on the partial column retrieval of O3, CO, CH4, and N2O. Sensitivities of the partial column, error, and degrees of freedom (DOFs) of each layer to different levels of ILS degradation for O3, CO, CH4, and N2O are estimated. We then evaluate the impact of ILS degradation on the long-term measurements. In addition, we derive the range of ILS degradation corresponding to the acceptable uncertainties of O3, CO, CH4, and N2O results. The results show that the uncertainties induced by the ILS degradation on the absolute value, error, and the DOFs of the partial column are altitude and gas species dependent. The uncertainties of the partial columns of O3 and CO are larger than those on CH4 and N2O. The stratospheric partial columns are more sensitive to the ILS degradation compared to the tropospheric part. Our result improves the understanding of the ILS degradation on the FTIR measurements, which is important for the quantification of the measurement uncertainties and minimizes the bias of the inter-comparison between different measurement platforms. This is especially useful for the validation of satellite observations, the data assimilation of chemical model simulations, and the quantification of the source/sink/trend from the FTIR measurements.

Building the COllaborative Carbon Column Observing Network (COCCON): Long term stability and ensemble performance of the EM27/SUN Fourier transform spectrometer

In a 3.5 year long study, the long term performance of a mobile Bruker EM27/SUN spectrometer, used for greenhouse gases observations, is checked with respect to a co-located reference Bruker IFS 125HR spectrometer, which is part of the Total Carbon Column Observing Network (TCCON). We find that the EM27/SUN is stable on timescales of several years, qualifying it as an useful supplement for the existing TCCON network in remote areas. For achieving consistent performance, such an extension requires careful testing of any spectrometers involved by application of common quality assurance measures. One major aim of the COllaborative Carbon Column Observing Network (COCCON) infrastructure is to provide these services to all EM27/SUN operators. In the framework of COCCON development, the performance of an ensemble of 30 EM27/SUN spectrometers was tested and found to be very uniform, enhanced by the centralized inspection performed at the Karlsruhe Institute of Technology prior to deployment. Taking into account measured instrumental line shape parameters for each spectrometer, the resulting average bias across the ensemble in XCO2 is 0.20 ppm, while it is 0.8 ppb for XCH4. As indicated by the executed long-term study on one device presented here, the remaining empirical calibration factor deduced for each individual instrument can be assumed constant over time. Therefore the application of these empirical factors is expected to further improve the EM27/SUN network conformity beyond the raw residual bias reported above.

The influence of instrumental line shape degradation on NDACC gas retrievals: total column and profile

We simulated instrumental line shape (ILS) degradations with respect to typical types of misalignment, and compared their influence on each NDACC (Network for Detection of Atmospheric Composition Change) gas. The sensitivities of the total column, the root mean square (rms) of the fitting residual, the total random uncertainty, the total systematic uncertainty, the total uncertainty, degrees of freedom for signal (DOFs), and the profile with respect to different levels of ILS degradation for all current standard NDACC gases, i.e. O3, HNO3, HCl, HF, ClONO2, CH4, CO, N2O, C2H6, and HCN, were investigated. The influence of an imperfect ILS on NDACC gases' retrieval was assessed, and the consistency under different meteorological conditions and solar zenith angles (SZAs) were examined. The study concluded that the influence of ILS degradation can be approximated by the linear sum of individual modulation efficiency (ME) amplitude influence and phase error (PE) influence. The PE influence is of secondary importance compared with the ME amplitude. Generally, the stratospheric gases are more sensitive to ILS degradation than the tropospheric gases, and the positive ME influence is larger than the negative ME. For a typical ILS degradation (10 %), the total columns of stratospheric gases O3, HNO3, HCl, HF, and ClONO2 changed by 1.9, 0.7, 4, 3, and 23 %, respectively, while the columns of tropospheric gases CH4, CO, N2O, C2H6, and HCN changed by 0.04, 2.1, 0.2, 1.1, and 0.75 %, respectively. In order to suppress the fractional difference in the total column for ClONO2 and other NDACC gases within 10 and 1 %, respectively, the maximum positive ME degradations for O3, HNO3, HCl, HF, ClONO2, CO, C2H6, and HCN should be less than 6, 15, 5, 5, 5, 5, 9, and 13 %, respectively; the maximum negative ME degradations for O3, HCl, and HF should be less than 6, 12, and 12 %, respectively; the influence of ILS degradation on CH4 and N2O can be regarded as being negligible.

The influence of instrumental line shape degradation on NDACC gas retrievals

Instrumental line shape (ILS) degradation can cause significant biases between global FTIR (Fourier transform infrared) networks if not properly treated. Currently, how ILS degradation influences the global NDACC (Network for Detection of Atmospheric Composition Change) gases retrieval and how much ILS deviation is acceptable for each NDACC gas are still not fully quantified. We simulated ILS degradations with respect to typical types of misalignment, and compared their influence on each NDACC gas. The sensitivities of total column, root mean square of fitting residual (RMS), total random uncertainty, total systematic uncertainty, total uncertainty, degrees of freedom for signal (DOFs), and profile with respect to different levels of ILS degradation for all current NDACC gases, i.e., O3, HNO3, HCl, HF, ClONO2, CH4, CO, N2O, C2H6, and HCN, were investigated. The influence of an imperfect ILS on NDACC gases retrieval were assessed, and the consistency under different meteorological conditions and solar zenith angles (SZA) were examined. The study concluded that the influence of ILS degradation can be approximated by the linear sum of individual modulation efficiency (ME) amplitude influence and phase error (PE) influence. The PE influence is of secondary importance compared with the ME amplitude influence. For total column retrieval, the stratospheric gases are more sensitive to ILS degradation than the tropospheric gases. For profile retrieval, the positive ME has more influence on tropospheric gases than the stratospheric gases. In contrast, the negative ME has more influence on stratospheric gases than the tropospheric gases. In order to suppress the influence on total column for ClONO2 and other NDACC gases within 10 % and 1 %, respectively, the permitted maximum ILS degradation for each NDACC gas was deduced (summarized in Table 5).