Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions

Significant reductions in stratospheric ozone occur inside the polar vortices each spring when chlorine radicals produced by heterogeneous reactions on cold particle surfaces in winter destroy ozone mainly in two catalytic cycles, the ClO dimer cycle and the ClO/BrO cycle. Chlorofluorocarbons (CFCs), which are responsible for most of the chlorine currently present in the stratosphere, have been banned by the Montreal Protocol and its amendments, and the ozone layer is predicted to recover to 1980 levels within the next few decades. During the same period, however, climate change is expected to alter the temperature, circulation patterns and chemical composition in the stratosphere, and possible geo-engineering ventures to mitigate climate change may lead to additional changes. To realistically predict the response of the ozone layer to such influences requires the correct representation of all relevant processes. The European project RECONCILE has comprehensively addressed remaining questions in the context of polar ozone depletion, with the objective to quantify the rates of some of the most relevant, yet still uncertain physical and chemical processes. To this end RECONCILE used a broad approach of laboratory experiments, two field missions in the Arctic winter 2009/10 employing the high altitude research aircraft M55-Geophysica and an extensive match ozone sonde campaign, as well as microphysical and chemical transport modelling and data assimilation. Some of the main outcomes of RECONCILE are as follows: (1) vortex meteorology: the 2009/10 Arctic winter was unusually cold at stratospheric levels during the six-week period from mid-December 2009 until the end of January 2010, with reduced transport and mixing across the polar vortex edge; polar vortex stability and how it is influenced by dynamic processes in the troposphere has led to unprecedented, synoptic-scale stratospheric regions with temperatures below the frost point; in these regions stratospheric ice clouds have been observed, extending over >106km2 during more than 3 weeks. (2) Particle microphysics: heterogeneous nucleation of nitric acid trihydrate (NAT) particles in the absence of ice has been unambiguously demonstrated; conversely, the synoptic scale ice clouds also appear to nucleate heterogeneously; a variety of possible heterogeneous nuclei has been characterised by chemical analysis of the non-volatile fraction of the background aerosol; substantial formation of solid particles and denitrification via their sedimentation has been observed and model parameterizations have been improved. (3) Chemistry: strong evidence has been found for significant chlorine activation not only on polar stratospheric clouds (PSCs) but also on cold binary aerosol; laboratory experiments and field data on the ClOOCl photolysis rate and other kinetic parameters have been shown to be consistent with an adequate degree of certainty; no evidence has been found that would support the existence of yet unknown chemical mechanisms making a significant contribution to polar ozone loss. (4) Global modelling: results from process studies have been implemented in a prognostic chemistry climate model (CCM); simulations with improved parameterisations of processes relevant for polar ozone depletion are evaluated against satellite data and other long term records using data assimilation and detrended fluctuation analysis. Finally, measurements and process studies within RECONCILE were also applied to the winter 2010/11, when special meteorological conditions led to the highest chemical ozone loss ever observed in the Arctic. In addition to quantifying the 2010/11 ozone loss and to understand its causes including possible connections to climate change, its impacts were addressed, such as changes in surface ultraviolet (UV) radiation in the densely populated northern mid-latitudes

Isotopic Fingerprinting: A Promising Tool for Coffee Authenticity Checks

Almost every physical or chemical process in nature favors certain light stable isotopes over others, and thereby leaves an isotopic “fingerprint” on the substances involved. Prominent examples are the evaporation and condensation of water, which act together to produce a global “map” of hydrogen and oxygen isotopes in rainwater. Environmental parameters including humidity and soil fertility influence the stable isotope compositions of carbon and nitrogen in plant tissues. Therefore, every agricultural product carries isotopic information regarding its geographical origin, growing conditions, treatment and others. This makes stable isotope analysis a powerful tool for disclosing food authenticity and to applying quality checks to a number of products (e.g., wine, honey, and vanilla). Here we recapitulate the principles of stable isotope analysis in general as well as some applications to coffee from the literature and present our recent measurements of carbon, nitrogen, hydrogen and oxygen isotopes on a well defined set of coffee samples

In situ observations of CH2Cl2 and CHCl3 show efficient transport pathways for very short-lived species into the lower stratosphere via the Asian and the North American summer monsoon

Efficient transport pathways for ozone-depleting very short-lived substances (VSLSs) from their source regions into the stratosphere are a matter of current scientific debate; however they have yet to be fully identified on an observational basis. Understanding the increasing impact of chlorine-containing VSLSs (Cl-VSLSs) on stratospheric ozone depletion is important in order to validate and improve model simulations and future predictions. We report on a transport study using airborne in situ measurements of the Cl-VSLSs dichloromethane (CH2Cl2) and trichloromethane (chloroform, CHCl3) to derive a detailed description of two transport pathways from (sub)tropical source regions into the extratropical upper troposphere and lower stratosphere (Ex-UTLS) in the Northern Hemisphere (NH) late summer. The Cl-VSLS measurements were obtained in the upper troposphere and lower stratosphere (UTLS) above western Europe and the midlatitude Atlantic Ocean in the frame of the WISE (Wave-driven ISentropic Exchange) aircraft campaign in autumn 2017 and are combined with the results from a three-dimensional simulation of a Lagrangian transport model as well as back-trajectory calculations. Compared to background measurements of similar age we find up to 150 % enhanced CH2Cl2 and up to 100 % enhanced CHCl3 mixing ratios in the extratropical lower stratosphere (Ex-LS). We link the measurements of enhanced CH2Cl2 and CHCl3 mixing ratios to emissions in the region of southern and eastern Asia. Transport from this area to the Ex-LS at potential temperatures in the range of 370–400 K takes about 6–11 weeks via the Asian summer monsoon anticyclone (ASMA). Our measurements suggest anthropogenic sources to be the cause of these strongly elevated Cl-VSLS concentrations observed at the top of the lowermost stratosphere (LMS). A faster transport pathway into the Ex-LS is derived from particularly low CH2Cl2 and CHCl3 mixing ratios in the UTLS. These low mixing ratios reflect weak emissions and a local seasonal minimum of both species in the boundary layer of Central America and the tropical Atlantic. We show that air masses uplifted by hurricanes, the North American monsoon, and general convection above Central America into the tropical tropopause layer to potential temperatures of about 360–370 K are transported isentropically within 5–9 weeks from the boundary layer into the Ex-LS. This transport pathway linked to the North American monsoon mainly impacts the middle and lower part of the LMS with particularly low CH2Cl2 and CHCl3 mixing ratios. In a case study, we specifically analyze air samples directly linked to the uplift by the Category 5 Hurricane Maria that occurred during October 2017 above the Atlantic Ocean. CH2Cl2 and CHCl3 have similar atmospheric sinks and lifetimes, but the fraction of biogenic emissions is clearly higher for CHCl3 than for the mainly anthropogenically emitted CH2Cl2; consequently lower CHCl3 : CH2Cl2 ratios are expected in air parcels showing a higher impact of anthropogenic emissions. The observed CHCl3 : CH2Cl2 ratio suggests clearly stronger anthropogenic emissions in the region of southern and eastern Asia compared to those in the region of Central America and the tropical Atlantic. Overall, the transport of strongly enhanced CH2Cl2 and CHCl3 mixing ratios from southern and eastern Asia via the ASMA is the main factor in increasing the chlorine loading from the analyzed VSLSs in the Ex-LS during the NH late summer. Thus, further increases in Asian CH2Cl2 and CHCl3 emissions, as frequently reported in recent years, will further increase the impact of Cl-VSLSs on stratospheric ozone depletion

Investigating the roles of the Asian monsoon, the North American monsoon, and Hurricanes for efficient transport of chlorinated short-lived species to the UTLS based on in situ observations

Chlorinated very short-lived substances (Cl-VSLS) are not controlled by the Montreal Protocol but the recent emission increase of the Cl-VSLS CH2Cl2 (Dichloromethane) and CHCl3 (Chloroform) is believed to significantly increase the stratospheric chlorine loading from VSLS. Provided efficient transport of Cl-VSLS from the source region into the stratosphere further emission increases could ultimately even cause a significant delay of the predicted recovery date of the ozone layer to pre-1980 values. During the WISE (Wave-driven ISentropic Exchange) campaign in autumn 2017 excessive probing of the UTLS (upper troposphere lower stratosphere) region above Western Europe and the Atlantic Ocean was conducted from aboard the HALO (High Altitude and Long range) research aircraft. We use real-time in situ WISE measurements of CH2Cl2 and CHCl3 from HAGAR-V (High Altitude Gas AnalyzeR &#8211; 5 channel version) in correlation with N2O from UMAQS (University of Mainz Airborne QCL Spectrometer), as well as CLaMS (Chemical Lagrangian Model of the Stratosphere) global 3-dimensional simulations of air mass origin tracers and backward trajectories to identify the most efficient transport mechanisms for Cl-VSLS entering the LS region in northern hemispheric summer.The WISE measurements reveal two distinct transport pathways into the UTLS region of particularly CH2Cl2-rich and CH2Cl2-poor air. CH2Cl2-rich air could be identified to be transported by the Asian summer monsoon within about 4-10 weeks from its source regions in Asia into the stratosphere above the Atlantic Ocean at around 380 K and above. CH2Cl2-poor air could be identified to be mainly uplifted to potential temperatures of about 365 K by the North American monsoon above the region of Central America with transport times of only 2-5 weeks. In addition, we could link backward trajectories of CH2Cl2-poor air in the LS region to be uplifted by the category 5 hurricane Maria in September 2017. Based on all analyzed WISE measurements, we found that almost all young (transport time The measurements of both CH2Cl2 and CHCl3 show the lowest stratospheric mixing ratios originating in the region of Central America and enhanced mixing ratios from Asia (enhancements > 100 % and > 50 %, respectively). However, the source distribution of CHCl3 is much less clear than that of CH2Cl2 and inconspicuous CH2Cl2 measurements can also contain enhanced CHCl3 mixing ratios. Nevertheless, the anthropogenic impact on CHCl3 -rich air from Asia is clearly visible in the measurements and we believe it is likely that a future increase of Asian CHCl3 emissions could lead to similarly large stratospheric enhancements as already observed for CH2Cl2. Consequently, this would further increase ozone depletion from stratospheric chlorine deposition of VSLS.</p

Reconstructing high-resolution in-situ vertical carbon dioxide profiles in the sparsely monitored Asian monsoon region

Atmospheric concentrations of the greenhouse gases carbon dioxide and nitrous oxide haveincreased substantially because of human activities. However, their sources in South Asia,which contribute strongly to the accelerating global growth of carbon dioxide and nitrousoxide, are poorly quantified. Here, we present aircraft measurements with high temporal andvertical resolution up to 20 km during the Asian summer monsoon where rapid upwardtransport of surface pollutants to greater altitudes occurs. Using Lagrangian model simulations, we successfully reconstruct observed carbon dioxide profiles leading to an improvedunderstanding of the vertical structure of carbon dioxide in the Asian monsoon region. Weshow that spatio-temporal patterns of carbon dioxide on the Indian subcontinent driven byregional flux variations rapidly propagate to approximately 13 km with slower ascent above.Enhanced carbon dioxide compared to the stratospheric background can be detected up to20 km. We suggest that the propagation of these signals from the surface to the stratospherecan be used to evaluate transport models and assess carbon dioxide fluxes in South Asia