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

Mapping the drivers of formaldehyde (HCHO) variability from 2015 to 2019 over eastern China: Insights from Fourier transform infrared observation and GEOS-Chem model simulation

The major air pollutant emissions have decreased, and the overall air quality has substantially improved across China in recent years as a consequence of active clean air policies for mitigating severe air pollution problems. As key precursors of formaldehyde (HCHO) and ozone (O3), the volatile organic compounds (VOCs) in China are still increasing due to the lack of mitigation measures for VOCs. In this study, we investigated the drivers of HCHO variability from 2015 to 2019 over Hefei, eastern China, by using ground-based high-resolution Fourier transform infrared (FTIR) spectroscopy and GEOS-Chem model simulation. Seasonal and interannual variabilities of HCHO over Hefei were analyzed and hydroxyl (OH) radical production rates from HCHO photolysis were evaluated. The relative contributions of emitted and photochemical sources to the observed HCHO were analyzed by using ground-level carbon monoxide (CO) and Ox (O3 Cnitrogen oxide (NO2)) as tracers for emitted and photochemical HCHO, respectively. Contributions of emission sources from various categories and geographical regions to the observed HCHO summer-time enhancements were determined by using a series of GEOS-Chem sensitivity simulations. The column-averaged dry air mole fractions of HCHO (XHCHO) reached a maximum monthly mean value of 1.10.27 ppbv in July and a minimum monthly mean value of 0.40.11 ppbv in January. The XHCHO time series from 2015 to 2019 over Hefei showed a positive change rate of 2.380.71% per year. The photochemical HCHO is the dominant source of atmospheric HCHO over Hefei for most of the year (68.1 %). In the studied years, the HCHO photolysis was an important source of OH radicals over Hefei during all sunlight hours of both summer and winter days. The oxidations of both methane (CH4) and nonmethane VOCs (NMVOCs) dominate the HCHO production over Hefei and constitute the main driver of its summertime enhancements. The NMVOCrelated HCHO summertime enhancements were dominated by the emissions within eastern China. The observed increasing change rate of HCHO from 2015 to 2019 over Hefei was attributed to the increase in photochemical HCHO resulting from increasing change rates of both CH4 and NMVOC oxidations, which overwhelmed the decrease in emitted HCHO. This study provides a valuable evaluation of recent VOC emissions and regional photochemical capacity in China. In addition, understanding the sources of HCHO is a necessary step for tackling air pollution in eastern China and mitigating the emissions of pollutants.