Atmospheric Chemical Ionization Mass Spectrometer Research Articles

The airborne mass spectrometer AIMS – Part 2: Measurements of trace gases with stratospheric or tropospheric origin in the UTLS

Abstract. Understanding the role of climate-sensitive trace gas variabilities in the upper troposphere and lower stratosphere region (UTLS) and their impact on its radiative budget requires accurate measurements. The composition of the UTLS is governed by transport and chemistry of stratospheric and tropospheric constituents, such as chlorine, nitrogen oxide and sulfur compounds. The Atmospheric chemical Ionization Mass Spectrometer AIMS has been developed to accurately measure a set of these constituents on aircraft by means of chemical ionization. Here we present a setup using SF5− reagent ions for the simultaneous measurement of trace gas concentrations of HCl, HNO3 and SO2 in the pptv to ppmv (10−12 to 10−6 mol mol−1) range with in-flight and online calibration called AIMS-TG (Atmospheric chemical Ionization Mass Spectrometer for measurements of trace gases). Part 1 of this paper (Kaufmann et al., 2016) reports on the UTLS water vapor measurements with the AIMS-H2O configuration. The instrument can be flexibly switched between two configurations depending on the scientific objective of the mission. For AIMS-TG, a custom-made gas discharge ion source has been developed for generation of reagent ions that selectively react with HCl, HNO3, SO2 and HONO. HNO3 and HCl are routinely calibrated in-flight using permeation devices; SO2 is continuously calibrated during flight adding an isotopically labeled 34SO2 standard. In addition, we report on trace gas measurements of HONO, which is sensitive to the reaction with SF5−. The detection limit for the various trace gases is in the low 10 pptv range at a 1 s time resolution with an overall uncertainty of the measurement of the order of 20 %. AIMS has been integrated and successfully operated on the DLR research aircraft Falcon and HALO (High Altitude LOng range research aircraft). As an example, measurements conducted during the TACTS/ESMVal (Transport and Composition of the LMS/UT and Earth System Model Validation) mission with HALO in 2012 are presented, focusing on a classification of tropospheric and stratospheric influences in the UTLS region. The combination of AIMS measurements with other measurement techniques yields a comprehensive picture of the sulfur, chlorine and reactive nitrogen oxide budget in the UTLS. The different trace gases measured with AIMS exhibit the potential to gain a better understanding of the trace gas origin and variability at and near the tropopause.

Level 2 processing for the imaging Fourier transform spectrometer GLORIA: derivation and validation of temperature and trace gas volume mixing ratios from calibrated dynamics mode spectra

Abstract. The Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) is an airborne infrared limb imager combining a two-dimensional infrared detector with a Fourier transform spectrometer. It was operated aboard the new German Gulfstream G550 High Altitude LOng Range (HALO) research aircraft during the Transport And Composition in the upper Troposphere/lowermost Stratosphere (TACTS) and Earth System Model Validation (ESMVAL) campaigns in summer 2012. This paper describes the retrieval of temperature and trace gas (H2O, O3, HNO3) volume mixing ratios from GLORIA dynamics mode spectra that are spectrally sampled every 0.625 cm−1. A total of 26 integrated spectral windows are employed in a joint fit to retrieve seven targets using consecutively a fast and an accurate tabulated radiative transfer model. Typical diagnostic quantities are provided including effects of uncertainties in the calibration and horizontal resolution along the line of sight. Simultaneous in situ observations by the Basic Halo Measurement and Sensor System (BAHAMAS), the Fast In-situ Stratospheric Hygrometer (FISH), an ozone detector named Fairo, and the Atmospheric chemical Ionization Mass Spectrometer (AIMS) allow a validation of retrieved values for three flights in the upper troposphere/lowermost stratosphere region spanning polar and sub-tropical latitudes. A high correlation is achieved between the remote sensing and the in situ trace gas data, and discrepancies can to a large extent be attributed to differences in the probed air masses caused by different sampling characteristics of the instruments. This 1-D processing of GLORIA dynamics mode spectra provides the basis for future tomographic inversions from circular and linear flight paths to better understand selected dynamical processes of the upper troposphere and lowermost stratosphere.

A quantitative analysis of stratospheric HCl, HNO3, and O3in the tropopause region near the subtropical jet

The effects of chemical two-way mixing on the Extratropical Transition Layer (ExTL) near the subtropical jet are investigated by stratospheric tracer-tracer correlations. To this end, in situ measurements were performed west of Africa (25-32 ◦ N) during the Transport and Composition of the Upper Troposphere Lower Stratosphere (UTLS)/Earth System Model Validation (TACTS/ESMVal) mission in August/September 2012. The Atmospheric chemical Ionization Mass Spectrometer sampling HCl and HNO3 was for the first time deployed on the new German High Altitude and Long range research aircraft (HALO). Measurements of O3, CO, European Centre for Medium-Range Weather Forecasts (ECMWF) analysis, and the tight correlation of the unambiguous tracer HCl to O3 and HNO3 in the lower stratosphere were used to quantify the stratospheric content of these species in the ExTL. With increasing distance from the tropopause, the stratospheric content increased from 10% to 100% with differing profiles for HNO 3 and O 3 . Tropospheric fractions of 20% HNO 3 and 40% O 3 were detected up to a distance of 30 K above the tropopause.

Evolution of CO2, SO2, HCl, and HNO3in the volcanic plumes from Etna

The volcanic plumes from degassing Etna (Italy) were extensively probed with instruments onboard the Deutsches Zentrum fur Luft- und Raumfahrt research aircraft Falcon during the contrail, volcano, and cirrus experiment CONCERT on 29/30 September 2011. Up to 10.4 ppmv SO2 and 0.3 ppmv HCl were detected with the atmospheric chemical ionization mass spectrometer AIMS at 3.1 km altitude and 20 km distance to the summit. HNO3 is the dominant reactive nitrogen component in the plumes. Linking aircraft and ground-based observations by Hybrid Single-Particle Lagrangian Integrated Trajectory dispersion modeling, we identify two crater plumes with different compositions primarily injected by the Bocca Nuova and North East craters. Uniquely, we follow their chemical evolution up to 5 h plume age. Our results show that CO2/SO2 and SO2/HCl molar ratios are stable in the ageing plumes. Hence, conversion of SO2 to H2SO4 and partitioning of HCl in acidic plume particles play a minor role at dry tropospheric conditions. Thus, these trace gases allow monitoring volcanic activity far from the crater.