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Aircraft-borne in situ measurements of the chemical aerosol composition were conducted in the Asian tropopause aerosol layer (ATAL) over the Indian subcontinent in the summer of 2017, covering particle sizes below ∼3 µm. We have implemented a recently developed aerosol mass spectrometer, which adopts the laser desorption technique as well as the thermal desorption method for quantitative bulk information (i.e., a modified Aerodyne AMS), aboard the high-altitude research aircraft M-55 Geophysica. The instrument was deployed in July and August 2017 during the StratoClim EU campaign (Stratospheric and upper tropospheric processes for better Climate predictions) over Nepal, India, Bangladesh, and the Bay of Bengal, covering altitudes up to 20 kma.s.l. For particles with diameters between 10 nm and ∼3 µm, the vertical profiles of aerosol number densities from the eight research flights show significant enhancements in the altitude range of the ATAL. We observed enhancements in the mass concentrations of particulate nitrate, ammonium, and organics in a similar altitude range between approximately 13 and 18 km (corresponding to 360 and 410 K potential temperature). By means of the two aerosol mass spectrometry techniques, we show that the particles in the ATAL mainly consist of ammonium nitrate (AN) and organics. The single-particle analysis from laser desorption and ionization mass spectrometry revealed that a significant particle fraction (up to 70 % of all analyzed particles by number) within the ATAL results from the conversion of inorganic and organic gas-phase precursors, rather than from the uplift of primary particles from below. This can be inferred from the fact that the majority of the particles encountered in the ATAL consisted solely of secondary substances, namely an internal mixture of nitrate, ammonium, sulfate, and organic matter. These particles are externally mixed with particles containing primary components as well. The single-particle analysis suggests that the organic matter within the ATAL and in the lower stratosphere (even above 420 K) can partly be identified as organosulfates (OS), in particular glycolic acid sulfate, which are known as components indicative for secondary organic aerosol (SOA) formation. Additionally, the secondary particles are smaller in size compared to those containing primary components (mainly potassium, metals, and elemental carbon). The analysis of particulate organics with the thermal desorption method shows that the degree of oxidation for particles observed in the ATAL is consistent with expectations about secondary organics that were subject to photochemical processing and aging. We found that organic aerosol was less oxidized in lower regions of the ATAL ( K) compared to higher altitudes (here 390–420 K). These results suggest that particles formed in the lower ATAL are uplifted by prevailing diabatic heating processes and thereby subject to extensive oxidative aging. Thus, our observations are consistent with the concept of precursor gases being emitted from regional ground sources, subjected to rapid convective uplift, and followed by secondary particle formation and growth in the upper troposphere within the confinement of the Asian monsoon anticyclone (AMA). As a consequence, the chemical composition of these particles largely differs from the aerosol in the lower stratospheric background and the Junge layer.

We report on the developments that enabled the field deployment of a fully automated aerosol mass spectrometer, especially designed for high-altitude measurements on unpressurized aircraft. The merits of the two main categories of real-time aerosol mass spectrometry, i.e. (a) single-particle laser desorption and ionization and (b) continuous thermal desorption and electron impact ionization of aerosols, have been integrated into one compact apparatus with the aim to perform in situ real-time analysis of aerosol chemical composition. The demonstrated instrument, named the ERICA (European Research Council Instrument for Chemical composition of Aerosols), operated successfully aboard the high-altitude research aircraft M-55 Geophysica at altitudes up to 20 km while being exposed to ambient conditions of very low atmospheric pressure and temperature. A primary goal of those field deployments was the in situ study of the Asian tropopause aerosol layer (ATAL). During 11 research flights, the instrument operated for more than 49 h and collected chemical composition information of more than 150 000 single particles combined with quantitative chemical composition analysis of aerosol particle ensembles. This paper presents in detail the technical characteristics of the main constituent parts of the instrument, as well as the design considerations for its integration into the aircraft and its autonomous operation in the upper troposphere and lower stratosphere (UTLS). Additionally, system performance data from the first field deployments of the instrument are presented and discussed, together with exemplary mass spectrometry data collected during those flights.

In this paper, we present the design, development, and characteristics of the novel aerosol mass spectrometer ERICA (ERC Instrument for Chemical composition of Aerosols; ERC – European Research Council) and selected results from the first airborne field deployment. The instrument combines two well-established methods of real-time in situ measurements of fine particle chemical composition. The first method is the laser desorption and ionization technique, or laser ablation technique, for single-particle mass spectrometry (here with a frequency-quadrupled Nd:YAG laser at λ = 266 nm). The second method is a combination of thermal particle desorption, also called flash vaporization, and electron impact ionization (like the Aerodyne aerosol mass spectrometer). The same aerosol sample flow is analyzed using both methods simultaneously, each using time-of-flight mass spectrometry. By means of the laser ablation, single particles are qualitatively analyzed (including the refractory components), while the flash vaporization and electron impact ionization technique provides quantitative information on the non-refractory components (i.e., particulate sulfate, nitrate, ammonia, organics, and chloride) of small particle ensembles. These techniques are implemented in two consecutive instrument stages within a common sample inlet and a common vacuum chamber. At its front end, the sample air containing the aerosol particles is continuously injected via an aerodynamic lens. All particles which are not ablated by the Nd:YAG laser in the first instrument stage continue their flight until they reach the second instrument stage and impact on the vaporizer surface (operated at 600 ∘C). The ERICA is capable of detecting single particles with vacuum aerodynamic diameters (dva) between ∼ 180 and 3170 nm (d50 cutoff). The chemical characterization of single particles is achieved by recording cations and anions with a bipolar time-of-flight mass spectrometer. For the measurement of non-refractory components, the particle size range extends from approximately 120 to 3500 nm (d50 cutoff; dva), and the cations are detected with a time-of-flight mass spectrometer. The compact dimensions of the instrument are such that the ERICA can be deployed on aircraft, at ground stations, or in mobile laboratories. To characterize the focused detection lasers, the ablation laser, and the particle beam, comprehensive laboratory experiments were conducted. During its first deployments the instrument was fully automated and operated during 11 research flights on the Russian high-altitude research aircraft M-55 Geophysica from ground pressure and temperature to 20 km altitude at 55 hPa and ambient temperatures as low as −86 ∘C. In this paper, we show that the ERICA is capable of measuring reliably under such conditions.

During the monsoon season of the year 2017 the airborne StratoClim mission took place in Kathmandu, Nepal, with eight mission flights of the M-55 Geophysica in the upper troposphere–lower stratosphere (UTLS) of the Asian monsoon anticyclone (AMA) over northern India, Nepal, and Bangladesh. More than 100 events of new particle formation (NPF) were observed. In total, more than 2 h of flight time was spent under NPF conditions as indicated by the abundant presence of nucleation-mode aerosols, i.e. with particle diameters dp smaller than 15 nm, which were detected in situ by means of condensation nuclei counting techniques. Mixing ratios of nucleation-mode particles (nnm) of up to ∼ 50 000 mg−1 were measured at heights of 15–16 km (θ ≈ 370 K). NPF was most frequently observed at ∼ 12–16 km altitude (θ ≈ 355–380 K) and mainly below the tropopause. Resulting nnm remained elevated (∼ 300–2000 mg−1) up to altitudes of ∼ 17.5 km (θ ≈ 400 K), while under NPF conditions the fraction (f) of sub-micrometre-sized non-volatile residues (dp > 10 nm) remained below 50 %. At ∼ 12–14 km (θ ≈ 355–365 K) the minimum of f (< 15 %) was found, and underneath, the median f generally remains below 25 %. The persistence of particles at nucleation-mode sizes is limited to a few hours, mainly due to coagulation, as demonstrated by a numerical simulation. The frequency of NPF events observed during StratoClim 2017 underlines the importance of the AMA as a source region for UTLS aerosols and for the formation and maintenance of the Asian tropopause aerosol layer (ATAL). The observed abundance of NPF-produced nucleation-mode particles within the AMA is not unambiguously attributable to (a) specific source regions in the boundary layer (according to backward trajectory analyses), or (b) the direct supply with precursor material by convective updraught (from correlations of NPF with carbon monoxide), or (c) the recent release of NPF-capable material from the convective outflow (according to air mass transport times in the tropical tropopause layer, TTL). Temperature anomalies with ΔT of 2 K (peak-to-peak amplitude), as observed at a horizontal wavelength of ∼ 70–100 km during a level flight of several hours, match with NPF detections and represent an additional mechanism for local increases in supersaturation of the NPF precursors. Effective precursor supply and widely distributed temperature anomalies within the AMA can explain the higher frequency of intense NPF observed during StratoClim 2017 than all previous NPF detections with COPAS (COndensation PArticle counting System) at TTL levels over Brazil, northern Australia, or West Africa.

We analyse aerosol particle composition measurements from five research missions between 2014 and 2018 to assess the meridional extent of particles containing meteoric material in the upper troposphere and lower stratosphere (UTLS). Measurements from the Jungfraujoch mountaintop site and a low-altitude aircraft mission show that meteoric material is also present within middle- and lower-tropospheric aerosol but within only a very small proportion of particles. For both the UTLS campaigns and the lower- and mid-troposphere observations, the measurements were conducted with single-particle laser ablation mass spectrometers with bipolar-ion detection, which enabled us to measure the chemical composition of particles in a diameter range of approximately 150 nm to 3 µm. The five UTLS aircraft missions cover a latitude range from 15 to 68∘ N, altitudes up to 21 km, and a potential temperature range from 280 to 480 K. In total, 338 363 single particles were analysed, of which 147 338 were measured in the stratosphere. Of these total particles, 50 688 were characterized by high abundances of magnesium and iron, together with sulfuric ions, the vast majority (48 610) in the stratosphere, and are interpreted as meteoric material immersed or dissolved within sulfuric acid. It must be noted that the relative abundance of such meteoric particles may be overestimated by about 10 % to 30 % due to the presence of pure sulfuric acid particles in the stratosphere which are not detected by the instruments used here. Below the tropopause, the observed fraction of the meteoric particle type decreased sharply with 0.2 %–1 % abundance at Jungfraujoch, and smaller abundances (0.025 %–0.05 %) were observed during the lower-altitude Canadian Arctic aircraft measurements. The size distribution of the meteoric sulfuric particles measured in the UTLS campaigns is consistent with earlier aircraft-based mass-spectrometric measurements, with only 5 %–10 % fractions in the smallest particles detected (200–300 nm diameter) but with substantial (> 40 %) abundance fractions for particles from 300–350 up to 900 nm in diameter, suggesting sedimentation is the primary loss mechanism. In the tropical lower stratosphere, only a small fraction (< 10 %) of the analysed particles contained meteoric material. In contrast, in the extratropics the observed fraction of meteoric particles reached 20 %–40 % directly above the tropopause. At potential temperature levels of more than 40 K above the thermal tropopause, particles containing meteoric material were observed in much higher relative abundances than near the tropopause, and, at these altitudes, they occurred at a similar abundance fraction across all latitudes and seasons measured. Above 440 K, the observed fraction of meteoric particles is above 60 % at latitudes between 20 and 42∘ N. Meteoric smoke particles are transported from the mesosphere into the stratosphere within the winter polar vortex and are subsequently distributed towards low latitudes by isentropic mixing, typically below a potential temperature of 440 K. By contrast, the findings from the UTLS measurements show that meteoric material is found in stratospheric aerosol particles at all latitudes and seasons, which suggests that either isentropic mixing is effective also above 440 K or that meteoric fragments may be the source of a substantial proportion of the observed meteoric material.

We present a novel and compact design of a constant-pressure inlet (CPI) developed for use in airborne aerosol mass spectrometry. In particular, the inlet system is optimized for aerodynamic lenses commonly used in aerosol mass spectrometers, in which efficient focusing of aerosol particles into a vacuum chamber requires a precisely controlled lens pressure, typically of a few hectopascals. The CPI device can also be used in condensation particle counters (CPCs), cloud condensation nucleus counters (CCNCs), and gas-phase sampling instruments across a wide range of altitudes and inlet pressures. The constant pressure is achieved by changing the inner diameter of a properly scaled O-ring that acts as a critical orifice. The CPI control keeps air pressure and thereby mass flow rate (≈0.1 L min−1) upstream of an aerodynamic lens constant, deviating at most by only ±2 % from a preset value. In our setup, a pressure sensor downstream of the O-ring maintains control of the pinch mechanism via a feedback loop and setpoint conditions are reached within seconds. The device was implemented in a few instruments, which were successfully operated on different research aircraft covering a wide range of ambient pressures, from sea level up to about 55 hPa. Details of operation and the quality of aerosol particle transmission were evaluated by laboratory experiments and in-flight data with a single-particle mass spectrometer.

The presence of multiple independent sensing parameters in a single device is the key conceptual advantage of sensor devices based on an organic thin film transistor (OTFT) over simple organic chemiresistors. Practically, however, these multiple parameters must first be extracted from the electrical characteristics of the OTFTs and, thus, they are not immediately apparent. To exploit the advantage of OTFT sensors, we require a measurement technology to extract these parameters in real time. Here, we introduce an efficient, cost-effective system that is a faster and more compact alternative to the expensive and cumbersome laboratory-based instruments currently available. The characterisation system presented here records the electric behaviour of OTFTs in the form of its "saturated transfer characteristics" multiple times per second for virtually unlimited periods of time, with the option to multiplex up to 20 devices in parallel. By applying a bespoke algorithm to the measured transfer characteristics, the system then extracts, in real time, several underlying transistor parameters (on- and off-current, threshold voltage, and charge carrier mobility). Tests were conducted on the example of a poly(thieno[3,2-b]thiophene) (PBTTT) OTFT exposed to ethanol vapour. The system extracts the underlying OTFT parameters with very low noise without introducing apparent correlations between independent parameters as an artefact.