MIPAS IMK/IAA CFC-11 (CCl3F) and CFC-12 (CCl2F2) measurements: accuracy, precision and long-term stability

Eckert, E. et. al.Profiles of CFC-11 (CCl3F) and CFC-12 (CCl2F2) of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the European satellite Envisat have been retrieved from versions MIPAS/4.61 to MIPAS/ 4.62 and MIPAS/5.02 to MIPAS/5.06 level-1b data using the scientific level-2 processor run by Karlsruhe Institute of Technology (KIT), Institute of Meteorology and Climate Research (IMK) and Consejo Superior de Investigaciones Científicas (CSIC), Instituto de Astrofísica de Andalucía (IAA). These profiles have been compared to measurements taken by the balloon-borne cryosampler, Mark IV (MkIV) and MIPAS-Balloon (MIPAS-B), the airborne MIPAS-STRatospheric aircraft (MIPAS-STR), the satellite-borne Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) and the High Resolution Dynamic Limb Sounder (HIRDLS), as well as the groundbased Halocarbon and other Atmospheric Trace Species (HATS) network for the reduced spectral resolution period (RR: January 2005-April 2012) of MIPAS. ACE-FTS, MkIV and HATS also provide measurements during the high spectral resolution period (full resolution, FR: July 2002-March 2004) and were used to validate MIPAS CFC-11 and CFC-12 products during that time, as well as profiles from the Improved Limb Atmospheric Spectrometer, ILAS-II. In general, we find that MIPAS shows slightly higher values for CFC-11 at the lower end of the profiles (below ∼15 km) and in a comparison of HATS ground-based data and MIPAS measurements at 3 km below the tropopause. Differences range from approximately 10 to 50 pptv (∼5-20 %) during the RR period. In general, differences are slightly smaller for the FR period. An indication of a slight high bias at the lower end of the profile exists for CFC-12 as well, but this bias is far less pronounced than for CFC-11 and is not as obvious in the relative differences between MIPAS and any of the comparison instruments. Differences at the lower end of the profile (below ∼15 km) and in the comparison of HATS and MIPAS measurements taken at 3 km below the tropopause mainly stay within 10-50 pptv (corresponding to ∼2-10%for CFCPublished 12) for the RR and the FR period. Between ∼15 and 30 km, most comparisons agree within 10-20 pptv (10-20 %), apart from ILAS-II, which shows large differences above ∼17 km. Overall, relative differences are usually smaller for CFC-12 than for CFC-11. For both species - CFC-11 and CFC-12 - we find that differences at the lower end of the profile tend to be larger at higher latitudes than in tropical and subtropical regions. In addition, MIPAS profiles have a maximum in their mixing ratio around the tropopause, which is most obvious in tropical mean profiles. Comparisons of the standard deviation in a quiescent atmosphere (polar summer) show that only the CFC-12 FR error budget can fully explain the observed variability, while for the other products (CFC-11 FR and RR and CFC-12 RR) only two-thirds to three-quarters can be explained. Investigations regarding the temporal stability show very small negative drifts in MIPAS CFC-11 measurements. These instrument drifts vary between ∼1 and 3% decade-1. For CFC-12, the drifts are also negative and close to zero up to ∼30 km. Above that altitude, larger drifts of up to ∼50% decade-1 appear which are negative up to ∼35 km and positive, but of a similar magnitude, above. © Author(s) 2016.IMK data analysis was supported by DLR under contract number 50EE0901. MIPAS level 1B data were provided by ESA. We acknowledge support by Deutsche Forschungsgemeinschaft and Open Access Publishing Fund of Karlsruhe Institute of Technology. The Atmospheric Chemistry Experiment (ACE), also known as SCISAT, is a Canadian-led mission mainly supported by the Canadian Space Agency and the Natural Sciences and Engineering Research Council of Canada. Work at the Jet Propulsion Laboratory, California Institute of Technology, was carried out under contract with the National Aeronautics and Space Administration. Data collection and analysis of MIPAS-STR data used here were supported by the EU-project RECONCILE (grant no. 15 226365-FP7-ENV-2008-1) and the BMBF-project ENVIVAL-Life (DLR grant no. 50EE0841).Peer reviewe

High H2 Sorption Energetics in Zeolitic Imidazolate Frameworks

A combined experimental and theoretical study of H2 sorption was carried out on two isostructural zeolitic imidazolate frameworks ZIFs , namely ZIF 68 and ZIF 69. The former consists of Zn2 ions that are coordinated to two 2 nitroimidazolate and two benzimidazolate linkers in a tetrahedral fashion, while 5 chlorobenzimidazolate is used in place of benzimidazolate in the latter compound. H2 sorption measurements showed that the two ZIFs display similar isotherms and isosteric heats of adsorption Qst . The experimental initial H2 Qst value for both ZIFs was determined to be 8.1 kJ mol 1, which is quite high for materials that do not contain exposed metal centers. Molecular simulations of H2 sorption in ZIF 68 and ZIF 69 confirmed the similar H2 sorption properties between the two ZIFs, but also suggest that H2 sorption is slightly favored in ZIF 68 with regards to uptake at 77 K 1.0 atm. This work also presents inelastic neutron scattering INS spectra for H2 sorbed in ZIFs for the first time. The spectra for ZIF 68 and ZIF 69 show a broad range of intensities starting from about 4 meV. The most favorable H2 sorption site in both ZIFs corresponds to a confined region between two adjacent 2 nitroimidazolate linkers. Two dimensional quantum rotation calculations for H2 sorbed at this site in ZIF 68 and ZIF 69 produced rotational transitions that are in accord with the lowest energy peak observed in the INS spectrum for the respective ZIFs. We found that the primary binding site for H2 in the two ZIFs generates high barriers to rotation for the adsorbed H2, which are greater than those in several metal organic frameworks MOFs which possess open metal sites. H2 sorption was also observed for both ZIFs in the vicinity of the nitro groups of the 2 nitroimidazolate linkers. This study highlights the constructive interplay of experiment and theory to elucidate critical details of the H2 sorption mechanism in these two isostructural ZIF

Anomalous magnetic ordering in PrBa_2Cu_3O_{7-y} single crystals: Evidence for magnetic coupling between the Cu and Pr sublattices

In Al-free PrBa_2Cu_3O_{7-y} single crystals the kink in the temperature dependence of magnetic susceptibility chi_{ab}(T), connected with Pr antiferromagnetic ordering, disappears after field cooling (FC) in a field H || ab-plane. The kink in chi_c(T) remains unchanged after FC in H || c-axis. As a possible explanation, freezing of the Cu magnetic moments, lying in the ab-plane, caused by FC in H || ab, hinders their reorientation and, due to coupling between the Pr and Cu(2) sublattices, ordering of the Pr^{3+} moments. A field induced phase transition and a field dependence of the Pr^{3+} ordering temperature have been found for both H || c and H || ab.Comment: 11 pages (LaTex with elsart.sty), 5 EPS figs. Accepted to Physica

Confirmation of Anomalous Dynamical Arrest in attractive colloids: a molecular dynamics study

Previous theoretical, along with early simulation and experimental, studies have indicated that particles with a short-ranged attraction exhibit a range of new dynamical arrest phenomena. These include very pronounced reentrance in the dynamical arrest curve, a logarithmic singularity in the density correlation functions, and the existence of `attractive' and `repulsive' glasses. Here we carry out extensive molecular dynamics calculations on dense systems interacting via a square-well potential. This is one of the simplest systems with the required properties, and may be regarded as canonical for interpreting the phase diagram, and now also the dynamical arrest. We confirm the theoretical predictions for re-entrance, logarithmic singularity, and give the first direct evidence of the coexistence, independent of theory, of the two coexisting glasses. We now regard the previous predictions of these phenomena as having been established.Comment: 15 pages,15 figures; submitted to Phys. Rev.

Effects of the antipsychotic quetiapine on sleep and breathing: a review of clinical findings and potential mechanisms

OnlinePublQuetiapine is an antipsychotic medication indicated for schizophrenia and bipolar disorder. However, quetiapine also has hypnotic properties and as such is increasingly being prescribed at low doses ‘off-label’ in people with insomnia symptoms. Pharmacologically, in addition to its dopaminergic properties, quetiapine also modulates multiple other transmitter systems involved in sleep/wake modulation and potentially breathing. However, very little is known about the impact of quetiapine on obstructive sleep apnoea (OSA), OSA endotypes including chemosensitivity, and control of breathing. Given that many people with insomnia also have undiagnosed OSA, it is important to understand the effects of quetiapine on OSA and its mechanisms. Accordingly, this concise review covers the existing knowledge on the effects of quetiapine on sleep and breathing. Further, we highlight the pharmacodynamics of quetiapine and its potential to alter key OSA endotypes to provide potential mechanistic insight. Finally, an agenda for future research priorities is proposed to fill the current key knowledge gaps.Cricket Fauska, Tarun Bastiampillai, Robert J. Adams, Gary Wittert, Danny J. Eckert, Kelly A. Loffle

Seasonal and interannual variations of HCN amounts in the upper troposphere and lower stratosphere observed by MIPAS

We present a HCN climatology of the years 2002-2012, derived from FTIR limb emission spectra measured with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on the ENVISAT satellite, with the main focus on biomass burning signatures in the upper troposphere and lower stratosphere. HCN is an almost unambiguous tracer of biomass burning with a tropospheric lifetime of 5-6 months and a stratospheric lifetime of about 2 years. The MIPAS climatology is in good agreement with the HCN distribution obtained by the spaceborne ACE-FTS experiment and with airborne in situ measurements performed during the INTEX-B campaign. The HCN amounts observed by MIPAS in the southern tropical and subtropical upper troposphere have an annual cycle peaking in October-November, i.e. 1-2 months after the maximum of southern hemispheric fire emissions. The probable reason for the time shift is the delayed onset of deep convection towards austral summer. Because of overlap of varying biomass burning emissions from South America and southern Africa with sporadically strong contributions from Indonesia, the size and strength of the southern hemispheric plume have considerable interannual variations, with monthly mean maxima at, for example, 14 km between 400 and more than 700 pptv. Within 1-2 months after appearance of the plume, a considerable portion of the enhanced HCN is transported southward to as far as Antarctic latitudes. The fundamental period of HCN variability in the northern upper troposphere is also an annual cycle with varying amplitude, which in the tropics peaks in May after and during the biomass burning seasons in northern tropical Africa and southern Asia, and in the subtropics peaks in July due to trapping of pollutants in the Asian monsoon anticyclone (AMA). However, caused by extensive biomass burning in Indonesia and by northward transport of part of the southern hemispheric plume, northern HCN maxima also occur around October/November in several years, which leads to semi-annual cycles. There is also a temporal shift between enhanced HCN in northern low and mid- to high latitudes, indicating northward transport of pollutants. Due to additional biomass burning at mid- and high latitudes, this meridional transport pattern is not as clear as in the Southern Hemisphere. Upper tropospheric HCN volume mixing ratios (VMRs) above the tropical oceans decrease to below 200 pptv, presumably caused by ocean uptake, especially during boreal winter and spring. The tropical stratospheric tape recorder signal with an apparently biennial period, which was detected in MLS and ACE-FTS data from mid-2004 to mid-2007, is corroborated by MIPAS HCN data. The tape recorder signal in the whole MIPAS data set exhibits periodicities of 2 and 4 years, which are generated by interannual variations in biomass burning. The positive anomalies of the years 2003, 2007 and 2011 are caused by succession of strongly enhanced HCN from southern hemispheric and Indonesian biomass burning in boreal autumn and of elevated HCN from northern tropical Africa and the AMA in subsequent spring and summer. The anomaly of 2005 seems to be due to springtime emissions from tropical Africa followed by release from the summertime AMA. The vertical transport time of the anomalies is 1 month or less between 14 and 17 km in the upper troposphere and 8-11 months between 17 and 25 km in the lower stratosphere

Dynamics in Colloidal Liquids near a Crossing of Glass- and Gel-Transition Lines

Within the mode-coupling theory for ideal glass-transitions, the mean-squared displacement and the correlation function for density fluctuations are evaluated for a colloidal liquid of particles interacting with a square-well potential for states near the crossing of the line for transitions to a gel with the line for transitions to a glass. It is demonstrated how the dynamics is ruled by the interplay of the mechanisms of arrest due to hard-core repulsion and due to attraction-induced bond formation as well as by a nearby higher-order glass-transition singularity. Application of the universal relaxation laws for the slow dynamics near glass-transition singularities explains the qualitative features of the calculated time dependence of the mean-squared displacement, which are in accord with the findings obtained in molecular-dynamics simulation studies by Zaccarelli et. al [Phys. Rev. E 66, 041402 (2002)]. Correlation functions found by photon-correlation spectroscopy in a micellar system by Mallamace et. al [Phys. Rev. Lett. 84, 5431 2000)] can be interpreted qualitatively as a crossover from gel to glass dynamics.Comment: 13 pages, 12 figure

Pond canopy cover: a resource gradient for anuran larvae

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/72395/1/j.1365-2427.2005.01497.x.pd

Seasonal and interannual variations of HCN amounts in the upper troposphere and lower stratosphere observed by MIPAS

We present a HCN climatology of the years 2002-2012, derived from FTIR limb emission spectra measured with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on the ENVISAT satellite, with the main focus on biomass burning signatures in the upper troposphere and lower stratosphere. HCN is an almost unambiguous tracer of biomass burning with a tropospheric lifetime of 5-6 months and a stratospheric lifetime of about 2 years. The MIPAS climatology is in good agreement with the HCN distribution obtained by the spaceborne ACE-FTS experiment and with airborne in situ measurements performed during the INTEX-B campaign. The HCN amounts observed by MIPAS in the southern tropical and subtropical upper troposphere have an annual cycle peaking in October-November, i.e. 1-2 months after the maximum of southern hemispheric fire emissions. The probable reason for the time shift is the delayed onset of deep convection towards austral summer. Because of overlap of varying biomass burning emissions from South America and southern Africa with sporadically strong contributions from Indonesia, the size and strength of the southern hemispheric plume have considerable interannual variations, with monthly mean maxima at, for example, 14 km between 400 and more than 700 pptv. Within 1-2 months after appearance of the plume, a considerable portion of the enhanced HCN is transported southward to as far as Antarctic latitudes. The fundamental period of HCN variability in the northern upper troposphere is also an annual cycle with varying amplitude, which in the tropics peaks in May after and during the biomass burning seasons in northern tropical Africa and southern Asia, and in the subtropics peaks in July due to trapping of pollutants in the Asian monsoon anticyclone (AMA). However, caused by extensive biomass burning in Indonesia and by northward transport of part of the southern hemispheric plume, northern HCN maxima also occur around October/November in several years, which leads to semi-annual cycles. There is also a temporal shift between enhanced HCN in northern low and mid- to high latitudes, indicating northward transport of pollutants. Due to additional biomass burning at mid- and high latitudes, this meridional transport pattern is not as clear as in the Southern Hemisphere. Upper tropospheric HCN volume mixing ratios (VMRs) above the tropical oceans decrease to below 200 pptv, presumably caused by ocean uptake, especially during boreal winter and spring. The tropical stratospheric tape recorder signal with an apparently biennial period, which was detected in MLS and ACE-FTS data from mid-2004 to mid-2007, is corroborated by MIPAS HCN data. The tape recorder signal in the whole MIPAS data set exhibits periodicities of 2 and 4 years, which are generated by interannual variations in biomass burning. The positive anomalies of the years 2003, 2007 and 2011 are caused by succession of strongly enhanced HCN from southern hemispheric and Indonesian biomass burning in boreal autumn and of elevated HCN from northern tropical Africa and the AMA in subsequent spring and summer. The anomaly of 2005 seems to be due to springtime emissions from tropical Africa followed by release from the summertime AMA. The vertical transport time of the anomalies is 1 month or less between 14 and 17 km in the upper troposphere and 8-11 months between 17 and 25 km in the lower stratosphere

Measurement of the polarisation of W bosons produced with large transverse momentum in pp collisions at sqrt(s) = 7 TeV with the ATLAS experiment

This paper describes an analysis of the angular distribution of W->enu and W->munu decays, using data from pp collisions at sqrt(s) = 7 TeV recorded with the ATLAS detector at the LHC in 2010, corresponding to an integrated luminosity of about 35 pb^-1. Using the decay lepton transverse momentum and the missing transverse energy, the W decay angular distribution projected onto the transverse plane is obtained and analysed in terms of helicity fractions f0, fL and fR over two ranges of W transverse momentum (ptw): 35 < ptw < 50 GeV and ptw > 50 GeV. Good agreement is found with theoretical predictions. For ptw > 50 GeV, the values of f0 and fL-fR, averaged over charge and lepton flavour, are measured to be : f0 = 0.127 +/- 0.030 +/- 0.108 and fL-fR = 0.252 +/- 0.017 +/- 0.030, where the first uncertainties are statistical, and the second include all systematic effects.Comment: 19 pages plus author list (34 pages total), 9 figures, 11 tables, revised author list, matches European Journal of Physics C versio