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International audience; Abstract. 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 characterization, open-path (OP) and cell measurements. We demonstrate that both methods can detect the small variations in 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 from 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.

The increasing use of intensive agricultural practices can lead to damaging consequences for the atmosphere through enhanced emissions of air pollutants. However, there are few direct measurements of the surface-atmosphere exchange of trace gases and water–soluble aerosols over agricultural grassland, particularly of reactive nitrogen compounds. In this study, we present measurements of the concentrations, fluxes and deposition velocities of the trace gases HCl, HONO, HNO3, SO2 and NH3, and their associated water-soluble aerosol counterparts Cl-, NO2-, NO3-, SO42-, NH4+ as determined hourly for one month in May–June 2016 over agricultural grassland near Edinburgh, UK, pre- and post- fertilisation. Measurements were made using the Gradient of Aerosols and Gases Online Registration (GRAEGOR) wet–chemical two–point gradient instrument. Emissions of NH3 peaked at 1460 ng m-2 s-1 three hours after fertilisation, with an emission of HONO peaking at 4.92 ng m-2 s-1 occurring five hours after fertilisation. Apparent emissions of NO3- aerosol were observed after fertilisation which, coupled with a divergence of HNO3 deposition velocity (Vd) from its theoretical maximum value, suggested the reaction of emitted NH3 with atmospheric HNO3 to form ammonium nitrate aerosol. The use of the conservative exchange fluxes of tot-NH4+ and tot-NO3- indicated net emission of tot-NO3-, implying a ground source of HNO3 after fertilisation. Daytime concentrations of HONO remained above the detection limit (30 ng m-3) throughout the campaign, suggesting a daytime source for HONO at the site. Whilst the mean Vd of NH4+ was with 0.93 mm/s in the range expected for the accumulation mode, the larger average Vd for Cl- (3.65 mm/s), NO3- (1.97 mm/s), SO42- (1.89 mm/s) reflected the contribution of a super-micron fraction and decreased with increasing PM2.5/PM10 ratio (a proxy measurement for aerosol size), providing evidence – although limited by the use of a proxy for aerosol size – of a size-dependence of aerosol deposition velocity for aerosol chemical compounds, which has been suggested from process orientated models of aerosol deposition.

The increasing use of intensive agricultural practices can lead to damaging consequences for the atmosphere through enhanced emissions of air pollutants. However, there are few direct measurements of the surface–atmosphere exchange of trace gases and water-soluble aerosols over agricultural grassland, particularly of reactive nitrogen compounds. In this study, we present measurements of the concentrations, fluxes and deposition velocities of the trace gases HCl, HONO, HNO3, SO2 and NH3 as well as their associated water-soluble aerosol counterparts Cl−, NO2-, NO3-, SO42- and NH4+ as determined hourly for 1 month in May–June 2016 over agricultural grassland near Edinburgh, UK, pre- and postfertilisation. Measurements were made using the Gradient of Aerosols and Gases Online Registrator (GRAEGOR) wet-chemistry two-point gradient instrument. Emissions of NH3 peaked at 1460 ngm-2s-1 3 h after fertilisation, with an emission of HONO peaking at 4.92 ngm-2s-1 occurring 5 h after fertilisation. Apparent emissions of NO3- aerosol were observed after fertilisation which, coupled with a divergence of HNO3 deposition velocity (Vd) from its theoretical maximum value, suggested the reaction of emitted NH3 with atmospheric HNO3 to form ammonium nitrate aerosol. The use of the conservative exchange fluxes of tot-NH4+ and tot-NO3- indicated net emission of tot-NO3-, implying a ground source of HNO3 after fertilisation. Daytime concentrations of HONO remained above the detection limit (30 ng m−3) throughout the campaign, suggesting a daytime source for HONO at the site. Whilst the mean Vd of NH4+ was 0.93 mm s−1 in the range expected for the accumulation mode, the larger average Vd for Cl− (3.65 mm s−1), NO3- (1.97 mm s−1) and SO42- (1.89 mm s−1) reflected the contribution of a super-micron fraction and decreased with increasing PM2.5∕PM10 ratio (a proxy measurement for aerosol size), providing evidence – although limited by the use of a proxy for aerosol size – of a size dependence of aerosol deposition velocity for aerosol chemical compounds, which has been suggested from process-orientated models of aerosol deposition.