Inter-comparison of stratospheric mean-meridional circulation and eddy mixing among six reanalysis data sets

The stratospheric mean-meridional circulation (MMC) and eddy mixing are compared among six meteorological reanalysis data sets: NCEP-NCAR, NCEP-CFSR, ERA-40, ERA-Interim, JRA-25, and JRA-55 for the period 1979–2012. The reanalysis data sets produced using advanced systems (i.e., NCEP-CFSR, ERA-Interim, and JRA-55) generally reveal a weaker MMC in the Northern Hemisphere (NH) compared with those produced using older systems (i.e., NCEP/NCAR, ERA-40, and JRA-25). The mean mixing strength differs largely among the data products. In the NH lower stratosphere, the contribution of planetary-scale mixing is larger in the new data sets than in the old data sets, whereas that of small-scale mixing is weaker in the new data sets. Conventional data assimilation techniques introduce analysis increments without maintaining physical balance, which may have caused an overly strong MMC and spurious small-scale eddies in the old data sets. At the NH mid-latitudes, only ERA-Interim reveals a weakening MMC trend in the deep branch of the Brewer–Dobson circulation (BDC). The relative importance of the eddy mixing compared with the mean-meridional transport in the subtropical lower stratosphere shows increasing trends in ERA-Interim and JRA-55; this together with the weakened MMC in the deep branch may imply an increasing age-of-air (AoA) in the NH middle stratosphere in ERA-Interim. Overall, discrepancies between the different variables and trends therein as derived from the different reanalyses are still relatively large, suggesting that more investments in these products are needed in order to obtain a consolidated picture of observed changes in the BDC and the mechanisms that drive them.

Rossby wave propagation tracks in southern hemisphere mean basic flows associated to generalized frosts over southern South America

Based on previous observational studies on cold extreme events over southern South America, some recent studies suggest a possible relationship between Rossby wave propagation remotely triggered and the occurrence of frost. Using the concept of linear theory of Rossby wave propagation, this paper analyzes the propagation of such waves in two different basic states that correspond to austral winters with maximum and minimum generalized frost frequency of occurrence in the Wet Pampa (central-northwest Argentina). In order to determine the wave trajectories, the ray tracing technique is used in this study. Some theoretical discussion about this technique is also presented. The analysis of the basic state, from a theoretical point of view and based on the calculation of ray tracings, corroborates that remotely excited Rossby waves is the mechanism that favors the maximum occurrence of generalized frosts. The basic state in which the waves propagate is what conditions the places where they are excited. The Rossby waves are excited in determined places of the atmosphere, propagating towards South America along the jet streams that act as wave guides, favoring the generation of generalized frosts. In summary, this paper presents an overview of the ray tracing technique and how it can be used to investigate an important synoptic event, such as frost in a specific region, and its relationship with the propagation of large scale planetary waves.

Effects of gamma ray bursts in Earth`s biosphere

We continue former work on the modeling of potential effects of Gamma Ray Bursts on Phanerozoic Earth. We focus on global biospheric effects of ozone depletion and model the spectral reduction of light by NO(2) formed in the stratosphere. We also illustrate the current complexities involved in the prediction of how terrestrial ecosystems would respond to this kind of burst. We conclude that more biological field and laboratory data are needed to reach even moderate accuracy in this modeling.

30 million years of Permian volcanism recorded in the Choiyoi igneous province (W Argentina) and their source for younger ash fall deposits in the Parana Basin: SHRIMP U-Pb zircon geochronology evidence

We present four SHRIMP U-Pb zircon ages for the Choiyoi igneous province from the San Rafael Block, central-western Argentina. Dated samples come from the Yacimiento Los Reyunos Formation (281.4 +/- 2.5 Ma) of the Cochico Group (Lower Choiyoi section: andesitic breccias, dacitic to rhyolitic ignimbrites and continental conglomerates). Agua de los Burros Formation (264.8 +/- 2.3 Ma and 264.5 +/- 3.0 Ma) and Cerro Carrizalito Formation (251.9 +/- 2.7 Ma Upper Choiyoi section: rhyolitic ignimbrites and pyroclastic flows) spanning the entire Permian succession of the Choiyoi igneous province. A single ziron from the El Imperial Formation, that is overlain unconformably by the Choiyoi succession, yielded an early Permian age (297.2 +/- 5.3 Ma). while the main detrital zircon population indicated an Ordovician age (453.7 +/- 8.1 Ma). The new data establishes a more precise Permian age (Artinskian-Lopingian) for the section studied spanning 30 Ma of volcanic activity. Volcanological observations for the Choiyoi succession support the occurrence of explosive eruptions of plinian to ultraplinian magnitudes, capable of injecting enormous volumes of tephra in the troposphere-stratosphere. The new SHRIMP ages indicate contemporaneity between the Choyoi succession and the upper part of the Parana Basin late Paleozoic section, from the Irad up to the Rio do Rasto formations, encompassing about 24 Ma. Geochemical data show a general congruence in compositional and tectonic settings between the volcanics and Parana Basin Permian ash fall derived layers of bentonites. Thickness and granulometry of ash fall layers broadly fit into the depletion curve versus distance from the remote source vent of ultraplinian eruptions. Thus, we consider that the Choiyoi igneous province was the source of ash fall deposits in the upper Permian section of the Parana Basin. Data presented here allow a more consistent correlation between tectono-volcanic Permian events along the paleo-Pacific margin of southwestern Gondwana and the geological evolution of neighboring Paleozoic foreland basins in South America and Africa. (C) 2010 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

An overview of the HIBISCUS campaign

The EU HIBISCUS project consisted of a series of field campaigns during the intense convective summers in 2001, 2003 and 2004 in the State of São Paulo in Brazil. Its objective was to investigate the impact of deep convection on the Tropical Tropopause Layer (TTL) and the lower stratosphere by providing a new set of observational data on meteorology, tracers of horizontal and vertical transport, water vapour, clouds, and chemistry in the tropical Upper Troposphere/Lower Stratosphere (UT/LS). This was achieved using short duration research balloons to study local phenomena associated with convection over land, and long-duration balloons circumnavigating the globe to study the contrast between land and oceans.Analyses of observations of short-lived tracers, ozone and ice particles show strong episodic local updraughts of cold air across the lapse rate tropopause up to 18 or 19 km (420-440 K) in the lower stratosphere by overshooting towers. The long duration balloon and satellite measurements reveal a contrast between the composition of the lower stratosphere over land and oceanic areas, suggesting significant global impact of such events. The overshoots are shown to be well captured by non-hydrostatic meso-scale Cloud Resolving Models indicating vertical velocities of 50-60 m s(-1) at the top of the Neutral Buoyancy Level (NBL) at around 14 km, but, in contrast, are poorly represented by global Chemistry-Transport Models (CTM) forced by Numerical Weather Forecast Models (NWP) underestimating the overshooting process. Finally, the data collected by the HIBISCUS balloons have allowed a thorough evaluation of temperature NWP analyses and reanalyses, as well as satellite ozone, nitrogen oxide, water vapour and bromine oxide measurements in the tropics.

Lightning characteristics observed by a VLF/LF lightning detection network (LINET) in Brazil, Australia, Africa and Germany

This paper describes lightning characteristics as obtained in four sets of lightning measurements during recent field campaigns in different parts of the world from mid-latitudes to the tropics by the novel VLF/LF (very low frequency/low frequency) lightning detection network (LINET). The paper gives a general overview on the approach, and a synopsis of the statistical results for the observation periods as a whole and for one special day in each region. The focus is on the characteristics of lightning which can specifically be observed by this system like intra-cloud and cloud-to-ground stroke statistics, vertical distributions of intra-cloud strokes or peak current distributions. Some conclusions regarding lightning produced NOx are also presented as this was one of the aims of the tropical field campaigns TROCCINOX (Tropical Convection, Cirrus and Nitrogen Oxides Experiment) and TroCCiBras (Tropical Convection and Cirrus Experiment Brazil) in Brazil during January/February 2005, SCOUT-O3 (Stratospheric-Climate Links with Emphasis on the Upper Troposphere and Lower Stratosphere) and TWP-ICE (Tropical Warm Pool-International Cloud Experiment) during November/December 2005 and January/February 2006, respectively, in the Darwin area in N-Australia, and of AMMA (African Monsoon Multidisciplinary Analyses) in W-Africa during June-November 2006.

NDACC/SAOZ UV-visible total ozone measurements: improved retrieval and comparison with correlative ground-based and satellite observations

Accurate long-term monitoring of total ozone is one of the most important requirements for identifying possible natural or anthropogenic changes in the composition of the stratosphere. For this purpose, the NDACC (Network for the Detection of Atmospheric Composition Change) UV-visible Working Group has made recommendations for improving and homogenizing the retrieval of total ozone columns from twilight zenith-sky visible spectrometers. These instruments, deployed all over the world in about 35 stations, allow measuring total ozone twice daily with limited sensitivity to stratospheric temperature and cloud cover. The NDACC recommendations address both the DOAS spectral parameters and the calculation of air mass factors (AMF) needed for the conversion of O-3 slant column densities into vertical column amounts. The most important improvement is the use of O-3 AMF look-up tables calculated using the TOMS V8 (TV8) O-3 profile climatology, that allows accounting for the dependence of the O-3 AMF on the seasonal and latitudinal variations of the O-3 vertical distribution. To investigate their impact on the retrieved ozone columns, the recommendations have been applied to measurements from the NDACC/SAOZ (Systeme d'Analyse par Observation Zenithale) network. The revised SAOZ ozone data from eight stations deployed at all latitudes have been compared to TOMS, GOMEGDP4, SCIAMACHY-TOSOMI, SCIAMACHY-OL3, OMI-TOMS, and OMI-DOAS satellite overpass observations, as well as to those of collocated Dobson and Brewer instruments at Observatoire de Haute Provence (44 degrees N, 5.5 degrees E) and Sodankyla (67 degrees N, 27 degrees E), respectively. A significantly better agreement is obtained between SAOZ and correlative reference ground-based measurements after applying the new O-3 AMFs. However, systematic seasonal differences between SAOZ and satellite instruments remain. These are shown to mainly originate from (i) a possible problem in the satellite retrieval algorithms in dealing with the temperature dependence of the ozone cross-sections in the UV and the solar zenith angle (SZA) dependence, (ii) zonal modulations and seasonal variations of tropospheric ozone columns not accounted for in the TV8 profile climatology, and (iii) uncertainty on the stratospheric ozone profiles at high latitude in the winter in the TV8 climatology. For those measurements mostly sensitive to stratospheric temperature like TOMS, OMI-TOMS, Dobson and Brewer, or to SZA like SCIAMACHY-TOSOMI, the application of temperature and SZA corrections results in the almost complete removal of the seasonal difference with SAOZ, improving significantly the consistency between all ground-based and satellite total ozone observations.

Combined characterisation of GOME and TOMS total ozone measurements from space using ground-based observations from the NDSC

Several years of total ozone measured from space by the ERS-2 GOME, the Earth Probe TOMS, and the ADEOS TOMS, are compared with high-quality ground-based observations associated with the Network for the Detection of Stratospheric Change (NDSC), over an extended latitude range and a variety of geophysical conditions. The comparisons with each spaceborne sensor are combined altogether for investigating their respective solar zenith angle (SZA) dependence, dispersion, and difference of sensitivity. The space- and ground-based data are found to agree within a few percent on average. However, the analysis highlights for both GOME and TOMS several sources of discrepancies: (i) a SZA dependence with TOMS beyond 80° SZA; (ii) a seasonal SZA dependence with GOME beyond 70° SZA; (iii) a difference of sensitivity with GOME at high latitudes; (iv) a difference of sensitivity to low ozone values between satellite and SAOZ sensors around the southern tropics; (v) a north/south difference of TOMS with the ground-based observations; and (vi) internal inconsistencies in GOME total ozone. © 2001 COSPAR. Published by Elsevier Science Ltd. All rights reserved.

Modelling study of the impact of deep convection on the utls air composition - Part I: Analysis of ozone precursors

The aim of this work is to study the local impact on the upper troposphere/lower stratosphere air composition of an extreme deep convective system. For this purpose, we performed a simulation of a convective cluster composed of many individual deep convective cells that occurred near Bauru (Brazil). The simulation is performed using the 3-D mesoscale model RAMS coupled on-line with a chemistry model. The comparisons with meteorological measurements show that the model produces meteorological fields generally consistent with the observations. The present paper (part I) is devoted to the analysis of the ozone precursors (CO, NO x and non-methane volatile organic compounds) and HO x in the UTLS. The simulation results show that the distribution of CO with altitude is closely related to the upward convective motions and consecutive outflow at the top of the convective cells leading to a bulge of CO between 7 km altitude and the tropopause (around 17km altitude). The model results for CO are consistent with satellite-borne measurements at 700 hPa. The simulation also indicates enhanced amounts of NO x up to 2 ppbv in the 7-17 km altitude layer mainly produced by the lightning associated with the intense convective activity. For insoluble non-methane volatile organic compounds, the convective activity tends to significantly increase their amount in the 7-17km layer by dynamical effects. During daytime in the presence of lightning NO x, this bulge is largely reduced in the upper part of the layer for reactive species (e.g. isoprene, ethene) because of their reactions with OH that is increased on average during daytime. Lightning NO x also impacts on the oxydizing capacity of the upper troposphere by reducing on average HO x, HO 2, H 2O 2 and organic hydroperoxides. During the simulation time, the impact of convection on the air composition of the lower stratosphere is negligible for all ozone precursors although several of the simulated convective cells nearly reach the tropopause. There is no significant transport from the upper troposphere to the lower stratosphere, the isentropic barrier not being crossed by convection. The impact of the increase of ozone precursors and HO x in the upper troposphere on the ozone budget in the LS is discussed in part II of this series of papers.

Cirrus clouds observation in Santa Maria, Rio Grande do Sul during the experiment Chuva - Sul.

Cirrus clouds are an interesting point in the research of the atmosphere due their behavior and the effect on the earth radiation budget. They can affect the atmospheric radiation budget by reflecting the incoming solar radiation and absorbing the outgoing terrestrial radiation. Also, this cloud type is involved in the dehydration of the upper troposphere and lower stratosphere. So, it is interesting to increment the measurements of this type of clouds from the ground. During November and December 2012, through the CHUVA-SUL campaign, measurements with lidar in Santa Maria, Rio Grande do Sul were conducted. The system installed in Santa Maria site (29.8 °S; 53.7 °W, 100 m asl) was a single elastic-backscatter lidar using the wavelength of 532 nm. Some days with cirrus clouds lidar measurements were detected. Four days with presence of cirrus cloud are showed in the present study. These days, 7, 8, 19 and 28 November 2012, was selected due the persistence of cirrus clouds over many hours. The raw retrieval lidar signals and inverted backscatter coefficient profiles were analyzed for the selected days. Base and top height was obtained by analysis of raw signal and backscatter coefficient. Extinction coefficient profiles were obtained by the assumption of the lidar ratio. Cirrus cloud optical depth (COD) values were calculated, from the integration of the extinction coefficient between the base and top altitudes of the cirrus clouds.

Retrieval of trace gases vertical profile in the lower atmosphere combining. Differential Optical Absorption Spectroscopy with radiative transfer models

The motivation for the work presented in this thesis is to retrieve profile information for the atmospheric trace constituents nitrogen dioxide (NO2) and ozone (O3) in the lower troposphere from remote sensing measurements. The remote sensing technique used, referred to as Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS), is a recent technique that represents a significant advance on the well-established DOAS, especially for what it concerns the study of tropospheric trace consituents. NO2 is an important trace gas in the lower troposphere due to the fact that it is involved in the production of tropospheric ozone; ozone and nitrogen dioxide are key factors in determining the quality of air with consequences, for example, on human health and the growth of vegetation. To understand the NO2 and ozone chemistry in more detail not only the concentrations at ground but also the acquisition of the vertical distribution is necessary. In fact, the budget of nitrogen oxides and ozone in the atmosphere is determined both by local emissions and non-local chemical and dynamical processes (i.e. diffusion and transport at various scales) that greatly impact on their vertical and temporal distribution: thus a tool to resolve the vertical profile information is really important. Useful measurement techniques for atmospheric trace species should fulfill at least two main requirements. First, they must be sufficiently sensitive to detect the species under consideration at their ambient concentration levels. Second, they must be specific, which means that the results of the measurement of a particular species must be neither positively nor negatively influenced by any other trace species simultaneously present in the probed volume of air. Air monitoring by spectroscopic techniques has proven to be a very useful tool to fulfill these desirable requirements as well as a number of other important properties. During the last decades, many such instruments have been developed which are based on the absorption properties of the constituents in various regions of the electromagnetic spectrum, ranging from the far infrared to the ultraviolet. Among them, Differential Optical Absorption Spectroscopy (DOAS) has played an important role. DOAS is an established remote sensing technique for atmospheric trace gases probing, which identifies and quantifies the trace gases in the atmosphere taking advantage of their molecular absorption structures in the near UV and visible wavelengths of the electromagnetic spectrum (from 0.25 μm to 0.75 μm). Passive DOAS, in particular, can detect the presence of a trace gas in terms of its integrated concentration over the atmospheric path from the sun to the receiver (the so called slant column density). The receiver can be located at ground, as well as on board an aircraft or a satellite platform. Passive DOAS has, therefore, a flexible measurement configuration that allows multiple applications. The ability to properly interpret passive DOAS measurements of atmospheric constituents depends crucially on how well the optical path of light collected by the system is understood. This is because the final product of DOAS is the concentration of a particular species integrated along the path that radiation covers in the atmosphere. This path is not known a priori and can only be evaluated by Radiative Transfer Models (RTMs). These models are used to calculate the so called vertical column density of a given trace gas, which is obtained by dividing the measured slant column density to the so called air mass factor, which is used to quantify the enhancement of the light path length within the absorber layers. In the case of the standard DOAS set-up, in which radiation is collected along the vertical direction (zenith-sky DOAS), calculations of the air mass factor have been made using “simple” single scattering radiative transfer models. This configuration has its highest sensitivity in the stratosphere, in particular during twilight. This is the result of the large enhancement in stratospheric light path at dawn and dusk combined with a relatively short tropospheric path. In order to increase the sensitivity of the instrument towards tropospheric signals, measurements with the telescope pointing the horizon (offaxis DOAS) have to be performed. In this circumstances, the light path in the lower layers can become very long and necessitate the use of radiative transfer models including multiple scattering, the full treatment of atmospheric sphericity and refraction. In this thesis, a recent development in the well-established DOAS technique is described, referred to as Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS). The MAX-DOAS consists in the simultaneous use of several off-axis directions near the horizon: using this configuration, not only the sensitivity to tropospheric trace gases is greatly improved, but vertical profile information can also be retrieved by combining the simultaneous off-axis measurements with sophisticated RTM calculations and inversion techniques. In particular there is a need for a RTM which is capable of dealing with all the processes intervening along the light path, supporting all DOAS geometries used, and treating multiple scattering events with varying phase functions involved. To achieve these multiple goals a statistical approach based on the Monte Carlo technique should be used. A Monte Carlo RTM generates an ensemble of random photon paths between the light source and the detector, and uses these paths to reconstruct a remote sensing measurement. Within the present study, the Monte Carlo radiative transfer model PROMSAR (PROcessing of Multi-Scattered Atmospheric Radiation) has been developed and used to correctly interpret the slant column densities obtained from MAX-DOAS measurements. In order to derive the vertical concentration profile of a trace gas from its slant column measurement, the AMF is only one part in the quantitative retrieval process. One indispensable requirement is a robust approach to invert the measurements and obtain the unknown concentrations, the air mass factors being known. For this purpose, in the present thesis, we have used the Chahine relaxation method. Ground-based Multiple AXis DOAS, combined with appropriate radiative transfer models and inversion techniques, is a promising tool for atmospheric studies in the lower troposphere and boundary layer, including the retrieval of profile information with a good degree of vertical resolution. This thesis has presented an application of this powerful comprehensive tool for the study of a preserved natural Mediterranean area (the Castel Porziano Estate, located 20 km South-West of Rome) where pollution is transported from remote sources. Application of this tool in densely populated or industrial areas is beginning to look particularly fruitful and represents an important subject for future studies.

Flugzeuggetragene Spurengasmessungen in der Tropopausenregion

ZusammenfassungIm Rahmen der EU-Projekte POLSTAR (Polar StratosphericAerosol Experiment) und STREAM (Stratosphere TroposphereExperiment by Airborne Measurements) wurden flugzeuggetragene Spurengasmessungen in verschiedenen geografischen Breiten durchgeführt. Zwei Messkampagnen fanden im Januar (POLSTAR 97) und März (STREAM 97) 1997 über Kiruna (Schweden, 67°N, 20°O) statt, eine Kampagne wurde im Juli 1998 von Timmins (Kanada, 47°N, 81°W) aus durchgeführt (STREAM 98).CO und N2O wurden mittels TDLAS (Tunable Diode Laser Absorption Spectroscopy) nachgewiesen, CO2 wurde mit einem modifizierten kommerziellen Messgerät breitbandig gemessen. Zur Untersuchung von Mischungsvorgängen in der Tropopausenregion wurden Korrelationenzwischen CO, O3, N2O, CO2 und NOy herangezogen.Dabei konnte festgestellt werden, dass im Winter in der untersten Stratosphäre Mischung mit troposphärischen Luftmassen durch isentropen Transport im Bereich der Polarfront bis zu potentiellen Temperaturen von Theta=335K auftritt. Im Sommer lässt sich Mischung mit troposphärischen Luftmassen bis mindestens Theta=360K nachweisen, die effektiver als im Winter abläuft.Exemplarisch kann an einem Flug gezeigt werden, dassbis Theta=349K die Ausbildung der Mischungsschicht durchLuftmassenaustausch an der Polarfront verursacht wird, während oberhalb von Theta=349K Signaturen subtropischertroposphärischer Luftmassen gefunden werden.Der stratosphärische Hintergrund wird mitbestimmt durch photochemisch gealterte Luftmassen, die ihren Ursprung höchstwahrscheinlich in der Vortexregion des vorangegangenen Winters haben.

GC/MS-Meßsystem für Nicht-Methan-Kohlenwasserstoffe

Im Rahmen der Projekte CARIBIC ('Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container') und INDOEX ('Indian Ocean Experi-ment') wurde ein Gaschromatograph mit Massenspektrometer zur Analyse von Luftproben auf Nicht-Methan-Kohlenwasserstoffe (NMKW) im ppb- und ppt-Bereich entwickelt. Während INDOEX erfolgte die Probennahme auf dem Forschungsschiff Ronald Brown, während CARIBIC mit einem automatischen Probensammler an Bord eines Passagierflugzeuges (Boeing 767-ER, LTU). Die NMKW-Meßergebnisse wurden zusammen mit Ergebnissen von Mes-sungen von Kohlenmonoxid (CO, einschließlich Isotopenzusam-mensetzung), Ozon (O3), Methan (CH4), Kohlendioxid (CO2), Distickstoffmonoxid (N2O), Schwefelhexafluorid (SF6) und Aerosoleigenschaften sowie meteorologischen Daten inter-pretiert. Während INDOEX (Februar / März 1999) wurde in der maritimen Grenzschicht (MBL) des Indischen Ozeans (IO) eine starke Variabilität diverser Spurengase beobachtet, die teilweise durch regionale Emissionen hervorgerufen wurde, die stärkste Variabilität war jedoch durch Langstrecken-transport aus mittleren Breiten der Nordhemisphäre bedingt. Aufgrund der Abweichungen vom klimatologischen Mittel, sollten regionale Quellen die MBL des IO im allgemeinen stärker beeinflussen. Die Einteilung des IO in meteorologi-sche Luftmassenregime wurde bestätigt. Starke Spurengasgra-dienten an der innertropischen Konvergenzzone (ITCZ) zeigen, daß die ITCZ in erster Linie den Austausch von Luftmassen zwischen den Hemisphären behindert. Bei CARIBIC werden Messungen von Spurengasen (ein-(schließlich NMKW) und Aerosoleigenschaften auf Flügen in der oberen Troposphäre / unteren Stratosphäre durchgeführt. Während eines Flug über Afrika wurden der Einfluß von durch Konvektion in die obere Troposphäre eingebrachten, frischen Abgasen aus Biomassenverbrennung nachgewiesen. Andere Luft-massen wurden durch Emissionen von Erdgas bzw. durch die Stratosphäre beeinflußt.

Development of the optimal estimation method for inversion of stratospheric emission spectra and validation of HNO3 profiles

This doctoral thesis focuses on ground-based measurements of stratospheric nitric acid (HNO3)concentrations obtained by means of the Ground-Based Millimeter-wave Spectrometer (GBMS). Pressure broadened HNO3 emission spectra are analyzed using a new inversion algorithm developed as part of this thesis work and the retrieved vertical profiles are extensively compared to satellite-based data. This comparison effort I carried out has a key role in establishing a long-term (1991-2010), global data record of stratospheric HNO3, with an expected impact on studies concerning ozone decline and recovery. The first part of this work is focused on the development of an ad hoc version of the Optimal Estimation Method (Rodgers, 2000) in order to retrieve HNO3 spectra observed by means of GBMS. I also performed a comparison between HNO3 vertical profiles retrieved with the OEM and those obtained with the old iterative Matrix Inversion method. Results show no significant differences in retrieved profiles and error estimates, with the OEM providing however additional information needed to better characterize the retrievals. A final section of this first part of the work is dedicated to a brief review on the application of the OEM to other trace gases observed by GBMS, namely O3 and N2O. The second part of this study deals with the validation of HNO3 profiles obtained with the new inversion method. The first step has been the validation of GBMS measurements of tropospheric opacity, which is a necessary tool in the calibration of any GBMS spectra. This was achieved by means of comparisons among correlative measurements of water vapor column content (or Precipitable Water Vapor, PWV) since, in the spectral region observed by GBMS, the tropospheric opacity is almost entirely due to water vapor absorption. In particular, I compared GBMS PWV measurements collected during the primary field campaign of the ECOWAR project (Bhawar et al., 2008) with simultaneous PWV observations obtained with Vaisala RS92k radiosondes, a Raman lidar, and an IR Fourier transform spectrometer. I found that GBMS PWV measurements are in good agreement with the other three data sets exhibiting a mean difference between observations of ~9%. After this initial validation, GBMS HNO3 retrievals have been compared to two sets of satellite data produced by the two NASA/JPL Microwave Limb Sounder (MLS) experiments (aboard the Upper Atmosphere Research Satellite (UARS) from 1991 to 1999, and on the Earth Observing System (EOS) Aura mission from 2004 to date). This part of my thesis is inserted in GOZCARDS (Global Ozone Chemistry and Related Trace gas Data Records for the Stratosphere), a multi-year project, aimed at developing a long-term data record of stratospheric constituents relevant to the issues of ozone decline and expected recovery. This data record will be based mainly on satellite-derived measurements but ground-based observations will be pivotal for assessing offsets between satellite data sets. Since the GBMS has been operated for more than 15 years, its nitric acid data record offers a unique opportunity for cross-calibrating HNO3 measurements from the two MLS experiments. I compare GBMS HNO3 measurements obtained from the Italian Alpine station of Testa Grigia (45.9° N, 7.7° E, elev. 3500 m), during the period February 2004 - March 2007, and from Thule Air Base, Greenland (76.5°N 68.8°W), during polar winter 2008/09, and Aura MLS observations. A similar intercomparison is made between UARS MLS HNO3 measurements with those carried out from the GBMS at South Pole, Antarctica (90°S), during the most part of 1993 and 1995. I assess systematic differences between GBMS and both UARS and Aura HNO3 data sets at seven potential temperature levels. Results show that, except for measurements carried out at Thule, ground based and satellite data sets are consistent within the errors, at all potential temperature levels.

Stable isotope investigations of atmospheric nitrous oxide

ZusammenfassungDie Analyse von Isotopenverhältnissen ist von wachsender Bedeutung bei der Untersuchung von Quellen, Senken und chemischen Reaktionswegen atmosphärischer Spurengase. Distickstoffoxid (N2O) hat vier isotopisch einfach substituierte Spezies: 14N15N16O, 15N14N16O, 14N217O und 14N218O. In der vorliegenden Arbeit wurden massenspektrometrische Methoden entwickelt, die eine komplette Charakterisierung der Variationen im Vorkommen dieser Spezies ermöglichen. Es wird die bisher umfassendste Darstellung dieser Variationen in Troposphäre und Stratosphäre gegeben und mit Bezug auf eine Reihe von Laborexperimenten detailliert interpretiert.Die Laborexperimente machen einen großen Anteil dieser Doktorarbeit aus und konzentrieren sich auf die Isotopenfraktionierung in den stratosphärischen N2O-Senken, d. h. Photolyse und Reaktion mit elektronisch angeregten Sauerstoffatomen, O(1D). Diese Prozesse sind von dominantem Einfluß auf die Isotopenzusammensetzung von atmosphärischem N2O. Potentiell wichtige Parameter wie Temperatur- und Druckvariationen, aber auch Veränderungen der Wellenlänge im Fall der Photolyse wurden berücksichtigt. Photolyse bei stratosphärisch relevanten Wellenlängen > 190 nm zeigte immer Anreicherungen von 15N in beiden Stickstoffatomen des verbleibenden N2O wie auch in 17O und 18O. Die Anreicherungen waren am mittelständigen N-Atom signifikant höher als am endständigen N (mit mittleren Werten für 18O) und stiegen zu größeren Wellenlängen und niedrigeren Temperaturen hin an. Erstmalig wurden für 18O und 15N am endständigen N-Atom Isotopenabreicherungen bei 185 nm-Photolyse festgestellt. Im Gegensatz zur Photolyse waren die Isotopenanreicherungen bei der zweiten wichtigen N2O-Senke, Reaktion mit O(1D) vergleichsweise gering. Jedoch war das positionsabhängige Fraktionierungsmuster dem der Photolyse direkt entgegengesetzt und zeigte größere Anreicherungen am endständigen N-Atom. Demgemäß führen beiden Senkenprozesse zu charakteristischen Isotopensignaturen in stratosphärischem N2O. Weitere N2O-Photolyseexperimente zeigten, daß 15N216O in der Atmosphäre höchstwahrscheinlich mit der statistisch zu erwartenden Häufigkeit vorkommt.Kleine stratosphärische Proben erforderten die Anpassung der massenspektrometrischen Methoden an Permanentflußtechniken, die auch für Messungen an Firnluftproben von zwei antarktischen Stationen verwendet wurden. Das 'Firnluftarchiv' erlaubte es, den gegenwärtigen Trend und die präindustriellen Werte der troposphärischen N2O-Isotopensignatur zu bestimmen. Ein daraus konstruiertes globales N2O-Isotopenbudget ist im Einklang mit den besten Schätzungen der Gesamt-N2O-Emissionen aus Böden und Ozeanen.17O-Messungen bestätigten die Sauerstoffisotopenanomalie in atmosphärischem N2O, zeigten aber auch, daß N2O-Photolyse die Sauerstoffisotope gemäß einem massenabhängigen Fraktionierungsgesetz anreichert. Eine troposphärische Ursache für einen Teil des Exzeß-17O wurde vorgeschlagen, basierend auf der Reaktion von NH2 mit NO2, wodurch die Sauerstoffisotopenanomalie von O3 über NO2 an N2O übertragen wird.