Precipitation of energetic particles into the atmosphere greatly disturbs the chemical composition from the upper stratosphere to the lower thermosphere. Most important are changes to the budget of ...atmospheric nitric oxides (NOx = N, NO, NO
2
) and to atmospheric reactive hydrogen oxides (HOx = H, OH, HO
2
), which both contribute to ozone loss in the stratosphere and mesosphere. The impact of energetic particle precipitation on the chemical composition of the atmosphere has been studied since the 1960s, and there are a number of observations as well as model studies concerning especially the auroral impact and large solar particle events. Changes to the NOx budget due to energetic particle precipitation can be quite long-lived during polar winter and can then be transported down into the lower mesosphere and stratosphere, where NOx is one of the main participants in catalytic ozone destruction. Energetic particle precipitation can also affect temperatures and dynamics of the atmosphere from the source region down to the stratosphere and possibly even down to the surface, due to a coupling of chemical composition changes affecting atmospheric heating and cooling rates, the mean circulation, and wave propagation and breaking. Thus, energetic particle precipitation impacts have been implemented in chemistry-climate models reaching from the surface up to the mesosphere or lower thermosphere. However, there are still a number of open questions in the theoretical description of the energetic particle precipitation impact; the most important are uncertainties in the formation rate of different NOx species due to energetic particle precipitation, and the complex coupling between chemical changes, atmospheric heating and cooling rates, and atmospheric dynamics.
Measurements from 2002 to 2011 by three independent satellite instruments, namely MIPAS, SABER, and SMR on board the ENVISAT, TIMED, and Odin satellites are used to investigate the intra-seasonal ...variability of stratospheric and mesospheric O3 volume mixing ratio (vmr) inside the Antarctic polar vortex due to solar and geomagnetic activity. In this study, we individually analysed the relative O3 vmr variations between maximum and minimum conditions of a number of solar and geomagnetic indices (F10.7 cm solar radio flux, Ap index, ≥ 2 MeV electron flux). The indices are 26-day averages centred at 1 April, 1 May, and 1 June while O3 is based on 26-day running means from 1 April to 1 November at altitudes from 20 to 70 km. During solar quiet time from 2005 to 2010, the composite of all three instruments reveals an apparent negative O3 signal associated to the geomagnetic activity (Ap index) around 1 April, on average reaching amplitudes between −5 and −10% of the respective O3 background. The O3 response exceeds the significance level of 95% and propagates downwards throughout the polar winter from the stratopause down to ~ 25 km. These observed results are in good qualitative agreement with the O3 vmr pattern simulated with a three-dimensional chemistry-transport model, which includes particle impact ionisation.
The 3‐D global chemistry and transport model (3dCTM) was used to investigate NO, OH, and O3 from January 2002 to May 2010 between 60 km and 133 km. Their daytime and nighttime mean zonal means ...(55°–75° geomagnetic latitude) were analyzed with respect to short‐term variations associated with particle precipitation. The corresponding ionization rates were derived from the 3‐D atmospheric ionization module Osnabrück (AIMOS), which is based on particle flux measurements. The trace gas variations with respect to their background were investigated by using a superposed epoch analysis. The 27 day signature associated with particle precipitation is found in NO, while it is only indicated in OH and O3 during winter. A varying solar spectrum associated with the 11 year solar cycle causes modifications of this signal up to 10%, while the main patterns are conserved. Published observations show a clear 27 day signal, qualitatively agreeing with the model results at altitudes >70 km except for O3 in Northern Hemisphere winter. Further differences occur with respect to the magnitude of the trace gas variations, primarily attributed to the different trace gas background and dynamical variations of the background atmosphere. Absolute OH variations are overestimated by the 3dCTM during winter, while the opposite is true for O3. These differences might originate from an unknown offset in AIMOS, incorrect chemical reaction rates, a different background of H2O and O3, and the model dynamics. However, their nonlinear relationship and their altitude of largest response are qualitatively captured in Southern Hemisphere winter.
Key Points
The 27 day solar rotational signal in atmospheric trace gas simulations induced by particle precipitation
Strong impact on trace gas response due to dynamical variability
Overestimation of particle impact but qualitatively captured chemistry involved in the model
Particle precipitation causes atmospheric ionization. Modeled ionization rates are widely used in atmospheric chemistry/climate simulations of the upper atmosphere. As ionization rates are based on ...particle measurements some assumptions concerning the energy spectrum are required. While detectors measure particles binned into certain energy ranges only, the calculation of a ionization profile needs a fit for the whole energy spectrum. Therefore the following assumptions are needed: (a) fit function (e.g. power-law or Maxwellian), (b) energy range, (c) amount of segments in the spectral fit, (d) fixed or variable positions of intersections between these segments. The aim of this paper is to quantify the impact of different assumptions on ionization rates as well as their consequences for atmospheric chemistry modeling.
As the assumptions about the particle spectrum are independent from the ionization model itself the results of this paper are not restricted to a single ionization model, even though the Atmospheric Ionization Module OSnabrück (Aimos, Wissing and Kallenrode, 2009) is used here. We include protons only as this allows us to trace changes in the chemistry model directly back to the different assumptions without the need to interpret superposed ionization profiles. However, since every particle species requires a particle spectrum fit with the mentioned assumptions the results are generally applicable to all precipitating particles.
The reader may argue that the selection of assumptions of the particle fit is of minor interest, but we would like to emphasize on this topic as it is a major, if not the main, source of discrepancies between different ionization models (and reality). Depending on the assumptions single ionization profiles may vary by a factor of 5, long-term calculations may show systematic over- or underestimation in specific altitudes and even for ideal setups the definition of the energy-range involves an intrinsic 25% uncertainty for the ionization rates.
The effects on atmospheric chemistry (HOx, NOx and Ozone) have been calculated by 3dCTM, showing that the spectrum fit is responsible for a 8% variation in Ozone between setups, and even up to 50% for extreme setups.
•Assumptions in the particle spectrum fit are responsible for major discrepancies in ionization rates.•The description of the energy range alone results in 25% uncertainty.•Ionization profiles of the same period may vary up to factor 5.•Systematic over- and underestimations at specific altitudes may be caused.•8% of the Ozone variation can be traced back to characteristics of the spectrum fit.
We present altitude-dependent lifetimes of NOx , determined with MIPAS/ENVISAT (the Michelson Interferometer for Passive Atmospheric Sounding/the European Environment Satellite), for the Southern ...polar region after the solar proton event in October-November 2003. Between 50° S and 90° S and decreasing in altitude they range from about two days at 64 km to about 20 days at 44 km. The lifetimes are controlled by transport, mixing and photochemistry. We infer estimates of dynamical lifetimes by comparison of the observed decay to photochemical lifetimes calculated with the SLIMCAT 3-D Model. Photochemical loss contributes to the observed NOx depletion by 0.1% at 44 km, increasing with altitude to 45% at 64 km. In addition, we show the correlation of modelled ionization rates and observed NOx densities under consideration of the determined lifetimes of NOx , and calculate altitude-dependent effective production rates of NOx due to ionization. For that we compare ionization rates of the AIMOS data base with the MIPAS measurements from 15 October-31 December 2003. We derive effective NOx -production rates to be applied to the AIMOS ionization rates which range from about 0.2 NOx -molecules per ion pair at 44 km to 0.7 NOx -molecules per ion pair at 62 km. These effective production rates are considerably lower than predicted by box model simulations which could hint at an overestimation of the modelled ionization rates.
We analyze the impact of energetic particle precipitation on the stratospheric nitrogen budget, ozone abundances and net radiative heating using results from three global chemistry-climate models ...considering solar protons and geomagnetic forcing due to auroral or radiation belt electrons. Two of the models cover the atmosphere up to the lower thermosphere, the source region of auroral NO production. Geomagnetic forcing in these models is included by prescribed ionization rates. One model reaches up to about 80 km, and geomagnetic forcing is included by applying an upper boundary condition of auroral NO mixing ratios parameterized as a function of geomagnetic activity. Despite the differences in the implementation of the particle effect, the resulting modeled NOy in the upper mesosphere agrees well between all three models, demonstrating that geomagnetic forcing is represented in a consistent way either by prescribing ionization rates or by prescribing NOy at the model top.Compared with observations of stratospheric and mesospheric NOy from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument for the years 2002–2010, the model simulations reproduce the spatial pattern and temporal evolution well. However, after strong sudden stratospheric warmings, particle-induced NOy is underestimated by both high-top models, and after the solar proton event in October 2003, NOy is overestimated by all three models. Model results indicate that the large solar proton event in October 2003 contributed about 1–2 Gmol (109 mol) NOy per hemisphere to the stratospheric NOy budget, while downwelling of auroral NOx from the upper mesosphere and lower thermosphere contributes up to 4 Gmol NOy. Accumulation over time leads to a constant particle-induced background of about 0.5–1 Gmol per hemisphere during solar minimum, and up to 2 Gmol per hemisphere during solar maximum. Related negative anomalies of ozone are predicted by the models in nearly every polar winter, ranging from 10–50 % during solar maximum to 2–10 % during solar minimum. Ozone loss continues throughout polar summer after strong solar proton events in the Southern Hemisphere and after large sudden stratospheric warmings in the Northern Hemisphere. During mid-winter, the ozone loss causes a reduction of the infrared radiative cooling, i.e., a positive change of the net radiative heating (effective warming), in agreement with analyses of geomagnetic forcing in stratospheric temperatures which show a warming in the late winter upper stratosphere. In late winter and spring, the sign of the net radiative heating change turns to negative (effective cooling). This spring-time cooling lasts well into summer and continues until the following autumn after large solar proton events in the Southern Hemisphere, and after sudden stratospheric warmings in the Northern Hemisphere.
We compare simulations from three high-top (with upper lid above 120 km) and five medium-top (with upper lid around 80 km) atmospheric models with observations of odd nitrogen (NOx = NO + NO2), ...temperature, and carbon monoxide from seven satellite instruments (ACE-FTS on SciSat, GOMOS, MIPAS, and SCIAMACHY on Envisat, MLS on Aura, SABER on TIMED, and SMR on Odin) during the Northern Hemisphere (NH) polar winter 2008/2009. The models included in the comparison are the 3-D chemistry transport model 3dCTM, the ECHAM5/MESSy Atmospheric Chemistry (EMAC) model, FinROSE, the Hamburg Model of the Neutral and Ionized Atmosphere (HAMMONIA), the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA), the modelling tools for SOlar Climate Ozone Links studies (SOCOL and CAO-SOCOL), and the Whole Atmosphere Community Climate Model (WACCM4). The comparison focuses on the energetic particle precipitation (EPP) indirect effect, that is, the polar winter descent of NOx largely produced by EPP in the mesosphere and lower thermosphere. A particular emphasis is given to the impact of the sudden stratospheric warming (SSW) in January 2009 and the subsequent elevated stratopause (ES) event associated with enhanced descent of mesospheric air. The chemistry climate model simulations have been nudged toward reanalysis data in the troposphere and stratosphere while being unconstrained above. An odd nitrogen upper boundary condition obtained from MIPAS observations has further been applied to medium-top models. Most models provide a good representation of the mesospheric tracer descent in general, and the EPP indirect effect in particular, during the unperturbed (pre-SSW) period of the NH winter 2008/2009. The observed NOx descent into the lower mesosphere and stratosphere is generally reproduced within 20 %. Larger discrepancies of a few model simulations could be traced back either to the impact of the models' gravity wave drag scheme on the polar wintertime meridional circulation or to a combination of prescribed NOx mixing ratio at the uppermost model layer and low vertical resolution. In March–April, after the ES event, however, modelled mesospheric and stratospheric NOx distributions deviate significantly from the observations. The too-fast and early downward propagation of the NOx tongue, encountered in most simulations, coincides with a temperature high bias in the lower mesosphere (0.2–0.05 hPa), likely caused by an overestimation of descent velocities. In contrast, upper-mesospheric temperatures (at 0.05–0.001 hPa) are generally underestimated by the high-top models after the onset of the ES event, being indicative for too-slow descent and hence too-low NOx fluxes. As a consequence, the magnitude of the simulated NOx tongue is generally underestimated by these models. Descending NOx amounts simulated with medium-top models are on average closer to the observations but show a large spread of up to several hundred percent. This is primarily attributed to the different vertical model domains in which the NOx upper boundary condition is applied. In general, the intercomparison demonstrates the ability of state-of-the-art atmospheric models to reproduce the EPP indirect effect in dynamically and geomagnetically quiescent NH winter conditions. The encountered differences between observed and simulated NOx, CO, and temperature distributions during the perturbed phase of the 2009 NH winter, however, emphasize the need for model improvements in the dynamical representation of elevated stratopause events in order to allow for a better description of the EPP indirect effect under these particular conditions.
Traditional chemotherapeutic drugs are often restricted by severe side effects and lack of tumor specificity. Peptide prodrugs cleavable by peptidases present in the tumor environment have been ...explored to improve the therapeutic index of cytotoxic drugs. One such prodrug of doxorubicin (Dox), CPI-0004Na N-succinyl-beta-alanyl-L-leucyl-L-alanyl-L-leucyl-Dox (sALAL-Dox) has been shown to have an improved antitumor efficacy profile with reduced toxicity compared with Dox in tumor xenograft models (V. Dubois et al., Cancer Res., 62: 2327-2331, 2002). In this study, we demonstrate that CD10, a cell surface metalloprotease expressed on a variety of tumor cell types, is capable of cleaving CPI-0004Na and related peptide prodrugs such as N-succinyl-beta-alanyl-L-isoleucyl-L-alanyl-L-leucyl-Dox (sAIAL-Dox). This proteolytic cleavage generates leucyl-Dox, which is capable of entering cells and generating intracellular Dox. In a (3)Hthymidine proliferation assay, analogues of CPI-0004Na showed a 100-300-fold increase in potency on CD10(+) cells compared with CD10(-) cells. Cytotoxicity of CPI-0004Na was inhibited by phosphoramidon, a known inhibitor of CD10 enzymatic activity. Furthermore, Chinese hamster ovary CHO-S cells, which are resistant to CPI-0004Na, could be sensitized to the cytotoxic effect of the prodrug by transfection of a CD10 cDNA. Tumor xenograft studies using LNCaP prostate tumor cells support the important role of CD10 in the antitumor efficacy of these prodrugs against tumors expressing CD10. CPI-0004Na and sAIAL-Dox achieved statistically significant 70% tumor growth inhibition at day 22. CD10 is expressed on many types of human tumors including B-cell lymphoma, leukemia, and prostate, breast, colorectal, and lung carcinomas; therefore, CD10-cleavable prodrugs may be effective in a range of different tumor types.
Four new taxoids were isolated from cell cultures of Taxus baccata. Their structures were elucidated by spectroscopic analyses. Two were the aglycones corresponding to previously isolated ...7-O-xylosides of taxol C 1 and 10-deacetyltaxol C 2. The third 3 had an N-methylated side-chain, while the fourth, named taxcultine 4, contained an n-propyl group on the side-chain. All four compounds actively promoted tubulin assembly. Taxol C 1 showed potent and selective cytotoxicity in the NCI human cell line screen.
A dedicated analysis of the muon-induced background in the EDELWEISS dark matter search has been performed on a data set acquired in 2009 and 2010. The total muon flux underground in the Laboratoire ...Souterrain de Modane (LSM) was measured to be Φμ=(5.4±0.2-0.9+0.5)muons/m2/d. The modular design of the μ-veto system allows the reconstruction of the muon trajectory and hence the determination of the angular dependent muon flux in LSM. The results are in good agreement with both MC simulations and earlier measurements. Synchronization of the μ-veto system with the phonon and ionization signals of the Ge detector array allowed identification of muon-induced events. Rates for all muon-induced events Γμ=(0.172±0.012)evts/(kgd) and of WIMP-like events Γμ–n=0.008-0.004+0.005evts/(kgd) were extracted. After vetoing, the remaining rate of accepted muon-induced neutrons in the EDELWEISS-II dark matter search was determined to be Γirredμ–n<6·10-4evts/(kgd) at 90% C.L. Based on these results, the muon-induced background expectation for an anticipated exposure of 3000kgd for EDELWEISS-III is N3000kgdμ–n<0.6 events.
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