Abstract. Production and use of many synthetic halogenated trace gases are regulated internationally because of their contribution to stratospheric ozone depletion or to climate change. In many applications they have been replaced by shorter-lived compounds which have become measurable in the atmosphere as emissions increased. Non-target monitoring of trace gases rather than targeted measurements of well-known substances is needed to keep up with such changes in the atmospheric composition. We regularly deploy gas chromatography (GC) coupled to time-of-flight mass spectrometry (TOF-MS) for analysis of flask air samples and in situ measurements at the Taunus Observatory, a site in central Germany. TOF-MS record data over a continuous mass range enable a retrospective analysis of the data set, which can thus be considered a type of digital air archive. This archive can be made use of if new substances come into use and their mass spectrometric fingerprint is identified. However, quantifying new replacement halocarbons can be challenging, as mole fractions are generally low, requiring high measurement precision and low detection limits. In addition, calibration can be demanding, as calibration gases may not contain sufficiently high amounts of newly used substances or the amounts in the calibration gas have not been quantified. This paper presents an indirect data evaluation approach for TOF-MS data, where the calibration is linked to another compound which could be quantified in the calibration gas. We also present an approach to evaluate the quality of the indirect calibration method and to select periods of stable instrument performance and well suited reference compounds. The method is applied to three short-lived synthetic halocarbons: HFO-1234-yf, HFO-1234ze(E), and HCFO-1233zd(E). They represent replacements for longer-lived HFCs and exhibit increasing mole fractions in the atmosphere. The indirectly calibrated results are compared to directly calibrated measurements using data from TOF-MS canister sample analysis and TOF-MS in situ measurements, which are available for some periods of our data set. The application of the indirect calibration method on several test cases can result into accuracies around 13 % to 20 %. For H(C)FOs accuracies up to 25 % are achieved. The indirectly calculated mole fractions of the investigated H(C)FOs at Taunus Observatory range between measured mole fractions at urban Dübendorf and Jungfraujoch stations in Switzerland.
Whole air samplers were flown on large balloons that were launched from Kiruna (67.9°N, 21.1°E) in the period from 30 November 1991 until 20 March 1992 during EASOE. Thirteen vertical profiles of the CCl 2 F 2 mixing ratio were obtained from the analyses of stratospheric air samples that were collected at altitudes between about 10 and 31 km. An empirical correlation function derived from simultaneous profile observations of CCl 2 F 2 and the five other most abundant organic chlorine species was used to determine the vertical distribution of total organic chlorine (Σ Cl org ) for each flight. These profiles allowed to estimate vertical profiles of the mixing ratio of total available chlorine, Cl y , and the temporal variation of its column abundance.
<p>The region around Southern Argentina and the Antarctic peninsula is known as the world&#8217;s strongest hotspot of stratospheric gravity wave activity. In this region, large tropospheric winds are perturbed by the orography of the Andes and the Antarctic peninsula resulting in the excitation of mountain waves which might propagate all the way up into the upper mesosphere when the polar night jet is intact. In addition, satellite observations also show large stratospheric wave activity in the region of the Drake passage, i.e., in between the Andes and the Antarctic peninsula, and along the corresponding latitudinal circle of 60&#176;S. The origin of these waves is currently not entirely understood. Several hypotheses are currently being investigated, like for example the idea that the mountain waves that were originally excited over the Andes and the Antarctic peninsula propagate horizontally to 60&#176;S and along the latitudinal circle. In order to investigate this and other hypotheses the German research aircraft HALO was deployed to Rio Grande, Tierra del Fuego, at the Southern Tip of Argentina in September and November 2019 in the frame of the SOUTHTRAC (Southern hemisphere Transport, Dynamics, and Chemistry) research mission. A total of 6 dedicated research flights with a typical length of 7000km were conducted to obtain gravity wave observations with the newly developed ALIMA (ALIMA=Airborne LIdar for Middle Atmosphere research)-instrument and the GLORIA (GLORIA=Gimballed Limb Observer for Radiance Imaging of the Atmosphere) limb sounder. While ALIMA measures temperatures and temperature perturbations in the altitude range from 20-90 km, GLORIA observations allow to characterize wave perturbations in temperatures and trace gas concentrations below flight level (<~14 km). This paper gives an overview of the mission objectives, the prevailing atmospheric conditions during the HALO deployment, and highlights some outstanding initial results of the gravity wave observations.</p>
Kurzfassung Lean Production-Methoden sind in der Praxis weit verbreitet. Unternehmen bewerten das Aufwand-Nutzen-Verhältnis der Methoden jedoch teilweise kritisch. Angesichts dieser Beurteilung stellt sich die Frage, wie sich der Aufwand von Lean-Methoden bewerten und reduzieren lässt. Dieser Beitrag beschreibt, wie Unternehmen ihren Aufwand für die Anwendung von Lean-Methoden strukturiert beurteilen und vermindern können.
Abstract. We present novel measurements of five short-lived brominated source gases (CH2Br2, CHBr3, CH2ClBr, CHCl2Br and CHClBr2). These rather short-lived gases are an important source of bromine to the stratosphere, where they can lead to depletion of ozone. The measurements have been obtained using an in situ gas chromatography and mass spectrometry (GC–MS) system on board the High Altitude and Long Range Research Aircraft (HALO). The instrument is extremely sensitive due to the use of chemical ionization, allowing detection limits in the lower parts per quadrillion (ppq, 10−15) range. Data from three campaigns using HALO are presented, where the upper troposphere and lower stratosphere (UTLS) of the northern hemispheric mid-to-high latitudes were sampled during winter and during late summer to early fall. We show that an observed decrease with altitude in the stratosphere is consistent with the relative lifetimes of the different compounds. Distributions of the five source gases and total organic bromine just below the tropopause show an increase in mixing ratio with latitude, in particular during polar winter. This increase in mixing ratio is explained by increasing lifetimes at higher latitudes during winter. As the mixing ratios at the extratropical tropopause are generally higher than those derived for the tropical tropopause, extratropical troposphere-to-stratosphere transport will result in elevated levels of organic bromine in comparison to air transported over the tropical tropopause. The observations are compared to model estimates using different emission scenarios. A scenario with emissions mainly confined to low latitudes cannot reproduce the observed latitudinal distributions and will tend to overestimate organic bromine input through the tropical tropopause from CH2Br2 and CHBr3. Consequently, the scenario also overestimates the amount of brominated organic gases in the stratosphere. The two scenarios with the highest overall emissions of CH2Br2 tend to overestimate mixing ratios at the tropical tropopause, but they are in much better agreement with extratropical tropopause mixing ratios. This shows that not only total emissions but also latitudinal distributions in the emissions are of importance. While an increase in tropopause mixing ratios with latitude is reproduced with all emission scenarios during winter, the simulated extratropical tropopause mixing ratios are on average lower than the observations during late summer to fall. We show that a good knowledge of the latitudinal distribution of tropopause mixing ratios and of the fractional contributions of tropical and extratropical air is needed to derive stratospheric inorganic bromine in the lowermost stratosphere from observations. In a sensitivity study we find maximum differences of a factor 2 in inorganic bromine in the lowermost stratosphere from source gas injection derived from observations and model outputs. The discrepancies depend on the emission scenarios and the assumed contributions from different source regions. Using better emission scenarios and reasonable assumptions on fractional contribution from the different source regions, the differences in inorganic bromine from source gas injection between model and observations is usually on the order of 1 ppt or less. We conclude that a good representation of the contributions of different source regions is required in models for a robust assessment of the role of short-lived halogen source gases on ozone depletion in the UTLS.
<p>Synthetic halocarbons are used for a wide range of applications, for example air conditioning or foam blowing. Many of them are long-lived greenhouse gases contributing to climate change and, in addition, may contribute to stratospheric ozone depletion if containing chlorine or bromine. Therefore, their production and use are regulated by the Montreal Protocol and its amendments. These long-lived halocarbons are increasingly replaced by a fourth generation of unsaturated short-lived halocarbons, the hydrochlorofluoroolefines (HCFOs) and hydrofluoroolefines (HFOs). The main removal process of these compounds in the atmosphere is reaction with OH radicals, and their average lifetimes are of the order of up to a few tens of days.</p><p>As part of the IAGOS-CARIBIC instrument package we operate an automated air sample collection system during regular flights in the upper troposphere and lowermost stratosphere. At altitudes around 10-12 km, samples are collected in stainless steel and glass flasks at predefined times. Post-flight laboratory analyses include gas chromatography - mass spectrometry measurements of a wide range of halocarbons. The short-lived compounds HFO-1234ze(E) and HCFO-1233zd(E) were detected in a small number of samples, indicating that these compounds are sufficiently long lived for transport into the upper troposphere. There were not found in stratospheric samples.</p><p>At this altitude, low abundance of OH and low temperatures may slow down chemical decay, and tracer lifetimes may increase significantly. Based on average temperatures and OH abundance, we estimate local lifetimes of HFO-1234ze(E) and HCFO-1233zd(E)&#160; in the mid-latitudes of up to 75 days and 200 days, respectively. Short-lived H(C)FOs reaching the upper troposphere could thus be transported over large distances and their degradation products may be deposited&#160; far from their emission sources.</p>
Abstract. This study presents a comprehensive and critical assessment of the meteorological conditions and atmospheric flow during the Lagrangian-type "Hill Cap Cloud Thuringia 2010" experiment (HCCT-2010). HCCT-2010 was performed in September and October 2010 at Mt. Schmücke in the Thuringian forest, Germany, applying three measurements sites (upwind, in-cloud, downwind) to study physical and chemical aerosol-cloud-interactions. A Lagrangian-type hill cap cloud experiment requires suitable cloud and particularly connected airflow conditions, i.e. representative air masses at the different measurement sites. Therefore, the present study aimed at the identification of time periods during the 6-weeks duration of the campaign, where such conditions were fulfilled and which can be used in further data examinations. The following topics were studied in detail: (i) the general synoptic weather situations including the mesoscale flow conditions by means of a classification of advected air masses and calculation of non-dimensional flow parameters (e.g. Froude number), (ii) local meteorological conditions, including synoptic front passages, the presence of orographic or frontal cloudiness, cloud base heights and vertical stratification, and (iii) local flow conditions by means of statistical analyses using the quasi-inert trace gas ozone and selected size bins of particle number size distributions as well as SF6 tracer experiments in the campaign area. A comprehensive analyses using statistical measures such as the COD (Coefficient Of Divergence) and cross-correlation have been carried out for the first time in the context of a Lagrangian-type hill cap cloud experiment. Suitable criteria for the aimed statistical analyses were thus developed and applied in the present study to characterise the local flow connectivity in detail. The comprehensive examination resulted in a total of 14 so-called "Full Cloud Events" (FCE), which are shown to conform to the Lagrange-type experimental philosophy of HCCT-2010. In addition, 15 so-called "Non-Cloud Events" (NCEs) could be established, which can be used as reference cases as they provide similarly suitable flow conditions but no cloud at the summit site. Orographic cloudiness was identified for approx. one third of the FCE periods, while about two thirds were associated to synoptic fronts. The statistical flow analyses indicate the existence of a strong link between the sites during the events, particularly under constant south-westerly flow conditions, high wind speeds and slightly stable stratification. The COD analyses using continuously measured concentrations of ozone and the 49 nm diameter particle bin revealed particularly for COD values below 0.1 very consistent time series, i.e. closely linked air masses between the different sites. The cross-correlation analysis revealed under connected flow conditions typical overflow times of about 15 to 30 min between the two valley sites. Additionally, the performed SF6 tracer experiments during the campaign clearly demonstrate that under appropriate meteorological conditions a Lagrangian-type approach is valid and that the connected flow validation procedure developed in this work is suitable for identifying such conditions. Finally, an overall evaluation of the identified FCEs is presented, which provides the basis for subsequent investigations of the measured chemical and physical data during HCCT-2010.
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