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The temperature of photovoltaic modules is modelled as a dynamic function of ambient temperature, shortwave and longwave irradiance and wind speed, in order to allow for a more accurate characterisation of their efficiency. A simple dynamic thermal model is developed by extending an existing parametric steady-state model using an exponential smoothing kernel to include the effect of the heat capacity of the system. The four parameters of the model are fitted to measured data from three photovoltaic systems in the Allgäu region in Germany using non-linear optimisation. The dynamic model reduces the root-mean-square error between measured and modelled module temperature to 1.58 K on average, compared to 3.03 K for the steady-state model, whereas the maximum instantaneous error is reduced from 20.02 to 6.58 K.

Spectral radiance measurements collected in nadir and sideward viewing directions by two airborne passive solar remote sensing instruments, the Spectral Modular Airborne Radiation measurement sysTem (SMART) and the Differential Optical Absorption Spectrometer (mini-DOAS), are used to compare the remote sensing results of cirrus optical thickness τ. The comparison is based on a sensitivity study using radiative transfer simulations (RTS) and on data obtained during three airborne field campaigns: the North Atlantic Rainfall VALidation (NARVAL) mission, the Mid-Latitude Cirrus Experiment (ML-CIRRUS) and the Aerosol, Cloud, Precipitation, and Radiation Interactions and Dynamics of Convective Cloud Systems (ACRIDICON) campaign. Radiative transfer simulations are used to quantify the sensitivity of measured upward radiance I with respect to τ, ice crystal effective radius reff, viewing angle of the sensor θV, spectral surface albedo α, and ice crystal shape. From the calculations it is concluded that sideward viewing measurements are generally better suited than radiance data from the nadir direction to retrieve τ of optically thin cirrus, especially at wavelengths larger than λ = 900 nm. Using sideward instead of nadir-directed spectral radiance measurements significantly improves the sensitivity and accuracy in retrieving τ, in particular for optically thin cirrus of τ ≤ 2. The comparison of retrievals of τ based on nadir and sideward viewing radiance measurements from SMART, mini-DOAS and independent estimates of τ from an additional active remote sensing instrument, the Water Vapor Lidar Experiment in Space (WALES), shows general agreement within the range of measurement uncertainties. For the selected example a mean τ of 0.54 ± 0.2 is derived from SMART, and 0.49 ± 0.2 by mini-DOAS nadir channels, while WALES obtained a mean value of τ = 0.32 ± 0.02 at 532 nm wavelength, respectively. The mean of τ derived from the sideward viewing mini-DOAS channels is 0.26 ± 0.2. For the few simultaneous measurements, the mini-DOAS sideward channel measurements systematically underestimate (−17.6 %) the nadir observations from SMART and mini-DOAS. The agreement between mini-DOAS sideward viewing channels and WALES is better, showing the advantage of using sideward viewing measurements for cloud remote sensing for τ ≤ 1. Therefore, we suggest sideward viewing measurements for retrievals of τ of thin cirrus because of the significantly enhanced capability of sideward viewing compared to nadir measurements.

A new retrieval algorithm for OSIRIS (Optical Spectrograph and Infrared Imager System) nitrogen dioxide (NO2) profiles is described and validated. The algorithm relies on spectral fitting to obtain slant column densities of NO2, followed by inversion using an algebraic reconstruction technique and the SaskTran spherical radiative transfer model (RTM) to obtain vertical profiles of local number density. The validation covers different latitudes (tropical to polar), years (2002–2012), all seasons (winter, spring, summer, and autumn), different concentrations of nitrogen dioxide (from denoxified polar vortex to polar summer), a range of solar zenith angles (68.6–90.5°), and altitudes between 10.5 and 39 km, thereby covering the full retrieval range of a typical OSIRIS NO2 profile. The use of a larger spectral fitting window than used in previous retrievals reduces retrieval uncertainties and the scatter in the retrieved profiles due to noisy radiances. Improvements are also demonstrated through the validation in terms of bias reduction at 15–17 km relative to the OSIRIS operational v3.0 algorithm. The diurnal variation of NO2 along the line of sight is included in a fully spherical multiple scattering RTM for the first time. Using this forward model with built-in photochemistry, the scatter of the differences relative to the correlative balloon NO2 profile data is reduced.

The Midlatitude Cirrus experiment (ML-CIRRUS) deployed the High Altitude and Long Range Research Aircraft (HALO) to obtain new insights into nucleation, life cycle, and climate impact of natural cirrus and aircraft-induced contrail cirrus. Direct observations of cirrus properties and their variability are still incomplete, currently limiting our understanding of the clouds’ impact on climate. Also, dynamical effects on clouds and feedbacks are not adequately represented in today’s weather prediction models. Here, we present the rationale, objectives, and selected scientific highlights of ML-CIRRUS using the G-550 aircraft of the German atmospheric science community. The first combined in situ–remote sensing cloud mission with HALO united state-of-the-art cloud probes, a lidar and novel ice residual, aerosol, trace gas, and radiation instrumentation. The aircraft observations were accompanied by remote sensing from satellite and ground and by numerical simulations. In spring 2014, HALO performed 16 flights above Europe with a focus on anthropogenic contrail cirrus and midlatitude cirrus induced by frontal systems including warm conveyor belts and other dynamical regimes (jet streams, mountain waves, and convection). Highlights from ML-CIRRUS include 1) new observations of microphysical and radiative cirrus properties and their variability in meteorological regimes typical for midlatitudes, 2) insights into occurrence of in situ–formed and lifted liquid-origin cirrus, 3) validation of cloud forecasts and satellite products, 4) assessment of contrail predictability, and 5) direct observations of contrail cirrus and their distinction from natural cirrus. Hence, ML-CIRRUS provides a comprehensive dataset on cirrus in the densely populated European midlatitudes with the scope to enhance our understanding of cirrus clouds and their role for climate and weather.

We report measurements of CH4 (measured in situ by the Harvard University Picarro Cavity Ringdown Spectrometer (HUPCRS) and NOAA Unmanned Aircraft System Chromatograph for Atmospheric Trace Species (UCATS) instruments), O3 (measured in situ by the NOAA dual-beam ultraviolet (UV) photometer), NO2, BrO (remotely detected by spectroscopic UV–visible (UV–vis) limb observations; see the companion paper of Stutz et al., 2016), and of some key brominated source gases in whole-air samples of the Global Hawk Whole Air Sampler (GWAS) instrument within the subtropical lowermost stratosphere (LS) and the tropical upper troposphere (UT) and tropopause layer (TTL). The measurements were performed within the framework of the NASA-ATTREX (National Aeronautics and Space Administration – Airborne Tropical Tropopause Experiment) project from aboard the Global Hawk (GH) during six deployments over the eastern Pacific in early 2013. These measurements are compared with TOMCAT/SLIMCAT (Toulouse Off-line Model of Chemistry And Transport/Single Layer Isentropic Model of Chemistry And Transport) 3-D model simulations, aiming at improvements of our understanding of the bromine budget and photochemistry in the LS, UT, and TTL.Changes in local O3 (and NO2 and BrO) due to transport processes are separated from photochemical processes in intercomparisons of measured and modeled CH4 and O3. After excellent agreement is achieved among measured and simulated CH4 and O3, measured and modeled [NO2] are found to closely agree with ≤ 15 ppt in the TTL (which is the detection limit) and within a typical range of 70 to 170 ppt in the subtropical LS during the daytime. Measured [BrO] ranges between 3 and 9 ppt in the subtropical LS. In the TTL, [BrO] reaches 0.5 ± 0.5 ppt at the bottom (150 hPa∕355 K∕14 km) and up to about 5 ppt at the top (70 hPa∕425 K∕18.5 km; see Fueglistaler et al., 2009 for the definition of the TTL used), in overall good agreement with the model simulations. Depending on the photochemical regime, the TOMCAT∕SLIMCAT simulations tend to slightly underpredict measured BrO for large BrO concentrations, i.e., in the upper TTL and LS. The measured BrO and modeled BrO ∕ Bryinorg ratio is further used to calculate inorganic bromine, Bryinorg. For the TTL (i.e., when [CH4] ≥ 1790 ppb), [Bryinorg] is found to increase from a mean of 2.63 ± 1.04 ppt for potential temperatures (θ) in the range of 350–360 K to 5.11 ± 1.57 ppt for θ = 390 − 400 K, whereas in the subtropical LS (i.e., when [CH4] ≤ 1790 ppb), it reaches 7.66 ± 2.95 ppt for θ in the range of 390–400 K. Finally, for the eastern Pacific (170–90° W), the TOMCAT/SLIMCAT simulations indicate a net loss of ozone of −0.3 ppbv day−1 at the base of the TTL (θ = 355 K) and a net production of +1.8 ppbv day−1 in the upper part (θ = 383 K).

The February–March 2014 deployment of the National Aeronautics and Space Administration (NASA) Airborne Tropical Tropopause Experiment (ATTREX) provided unique in situ measurements in the western Pacific tropical tropopause layer (TTL). Six flights were conducted from Guam with the long-range, high-altitude, unmanned Global Hawk aircraft. The ATTREX Global Hawk payload provided measurements of water vapor, meteorological conditions, cloud properties, tracer and chemical radical concentrations, and radiative fluxes. The campaign was partially coincident with the Convective Transport of Active Species in the Tropics (CONTRAST) and the Coordinated Airborne Studies in the Tropics (CAST) airborne campaigns based in Guam using lower-altitude aircraft (see companion articles in this issue). The ATTREX dataset is being used for investigations of TTL cloud, transport, dynamical, and chemical processes, as well as for evaluation and improvement of global-model representations of TTL processes. The ATTREX data are publicly available online (at https://espoarchive.nasa.gov/).

In order to improve our current knowledge on the budgets of the two most important anthropogenic greenhouse gases, CO2 and CH4, a co-ordinated measurement campaign in the Central European region was successfully carried out in May/June 2018 with the German research aircraft HALO and two smaller Cessna aircraft as its main experimental platforms. The goal of CoMet is to combine a suite of state-of-the-art airborne active (lidar) and passive remote sensors (spectrometer) with in-situ instruments to provide regional-scale data about greenhouse gases (GHGs) which are urgently required for their accurate modelling.

Novel airborne in situ measurements of inorganic chlorine, nitrogen oxide species, and ozone were performed inside the lower Antarctic polar vortex and at its edge in September 2012. We focus on one flight during the Transport and Composition of the LMS/Earth System Model Validation (TACTS/ESMVal) campaign with the German research aircraft HALO (High-Altitude LOng range research aircraft), reaching latitudes of 65°S and potential temperatures up to 405 K. Using the early winter correlations of reactive trace gases with N2O from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), we find high depletion of chlorine reservoir gases up to ∼40% (0.8 ppbv) at 12 km to 14 km altitude in the vortex and 0.4 ppbv at the edge in subsided stratospheric air with mean ages up to 4.5 years. We observe denitrification of up to 4 ppbv, while ozone was depleted by 1.2 ppmv at potential temperatures as low as 380 K. The advanced instrumentation aboard HALO enables high-resolution measurements with implications for the oxidation capacity of the lowermost stratosphere.

The absorption cross section of N2O5, σN2O5(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 + BrONO2 + HNO3) photochemistry and a non-linear least square fitting of the model result to the NO2 observations. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding – Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the σN2O5(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200–260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260–350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σN2O5(λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2–0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

Between 1 September and 4 October 2014, a combined airborne and ground-based measurement campaign was conducted to study tropical deep convective clouds over the Brazilian Amazon rain forest. The new German research aircraft, High Altitude and Long Range Research Aircraft (HALO), a modified Gulfstream G550, and extensive ground-based instrumentation were deployed in and near Manaus (State of Amazonas). The campaign was part of the German–Brazilian Aerosol, Cloud, Precipitation, and Radiation Interactions and Dynamics of Convective Cloud Systems–Cloud Processes of the Main Precipitation Systems in Brazil: A Contribution to Cloud Resolving Modeling and to the GPM (Global Precipitation Measurement) (ACRIDICON– CHUVA) venture to quantify aerosol–cloud–precipitation interactions and their thermodynamic, dynamic, and radiative effects by in situ and remote sensing measurements over Amazonia. The ACRIDICON–CHUVA field observations were carried out in cooperation with the second intensive operating period of Green Ocean Amazon 2014/15 (GoAmazon2014/5). In this paper we focus on the airborne data measured on HALO, which was equipped with about 30 in situ and remote sensing instruments for meteorological, trace gas, aerosol, cloud, precipitation, and spectral solar radiation measurements. Fourteen research flights with a total duration of 96 flight hours were performed. Five scientific topics were pursued: 1) cloud vertical evolution and life cycle (cloud profiling), 2) cloud processing of aerosol particles and trace gases (inflow and outflow), 3) satellite and radar validation (cloud products), 4) vertical transport and mixing (tracer experiment), and 5) cloud formation over forested/deforested areas. Data were collected in near-pristine atmospheric conditions and in environments polluted by biomass burning and urban emissions. The paper presents a general introduction of the ACRIDICON– CHUVA campaign (motivation and addressed research topics) and of HALO with its extensive instrument package, as well as a presentation of a few selected measurement results acquired during the flights for some selected scientific topics.

Observations of atmospheric trace gases in the tropical upper troposphere (UT), tropical tropopause layer (TTL), and lower stratosphere (LS) require dedicated measurement platforms and instrumentation. Here we present a new limb-scanning Differential Optical Absorption Spectroscopy (DOAS) instrument developed for NASA's Global Hawk (GH) unmanned aerial system and deployed during the Airborne Tropical TRopopause EXperiment (ATTREX). The mini-DOAS system is designed for automatic operation under unpressurized and unheated conditions at 14–18 km altitude, collecting scattered sunlight in three wavelength windows: UV (301–387 nm), visible (410–525 nm), and near infrared (900–1700 nm). A telescope scanning unit allows selection of a viewing angle around the limb, as well as real-time correction of the aircraft pitch. Due to the high altitude, solar reference spectra are measured using diffusors and direct sunlight. The DOAS approach allows retrieval of slant column densities (SCDs) of O3, O4, NO2, and BrO with relative errors similar to other aircraft DOAS systems. Radiative transfer considerations show that the retrieval of trace gas mixing ratios from the observed SCD based on O4 observations, the most common approach for DOAS measurements, is inadequate for high-altitude observations. This is due to the frequent presence of low-altitude clouds, which shift the sensitivity of the O4 SCD into the lower atmosphere and make it highly dependent on cloud coverage. A newly developed technique that constrains the radiative transfer by comparing in situ and DOAS O3 observations overcomes this issue. Extensive sensitivity calculations show that the novel O3-scaling technique allows the retrieval of BrO and NO2 mixing ratios at high accuracies of 0.5 and 15 ppt, respectively. The BrO and NO2 mixing ratios and vertical profiles observed during ATTREX thus provide new insights into ozone and halogen chemistry in the UT, TTL, and LS.

Spectral radiance measurements from two airborne passive solar remote sensing instruments, the Spectral Modular Airborne Radiation measurement sysTem (SMART) and the Differential Optical Absorption Spectrometer (mini-DOAS), are used to compare the remote sensing of cirrus optical thickness τ in nadir and off-nadir geometry. The comparison is based on a sensitivity study using radiative transfer simulations and on measurements during the North Atlantic Rainfall VALidation (NARVAL) mission, the Mid-Latitude Cirrus Experiment (ML-CIRRUS) and the Aerosol, Cloud, Precipitation, and Radiation Interactions and Dynamics of Convective Cloud Systems (ACRIDICON) campaign. Radiative transfer simulations are used to quantify the sensitivity of measured upward radiance I with respect to cirrus optical thickness τ, effective radius τeff, viewing angle of the sensor σL, surface albedo α and ice crystal shape. From the calculations it is concluded that off-nadir measurements at wavelengths larger than λ = 900 nm significantly improve the ability to measure clouds of low optical thickness. The comparison of nadir and off-nadir retrievals of τ from mini-DOAS, SMART and independent estimates by the Water Vapour Lidar Experiment in Space (WALES) show general agreement within the range of measurement uncertainties. For the selected example case a mean optical thickness of 0.54±0.2 is derived by SMART and 0.49±0.2 by mini-DOAS nadir channels, while WALES obtained a mean value of 0.32 at 532 nm wavelength respectively. The mean of τ derived from the scanning mini-DOAS channels is 0.26. For the few simultaneous measurements, the scanning mini-DOAS measurements systematically underestimate (−17.6 %) the nadir observations from SMART and mini-DOAS, most likely due to the different probed scenes. The different values of τ derived by SMART, mini-DOAS and WALES can be potentially linked to spatial averages, ice crystal shape and the measurement strategies. The agreement of the simulations and retrievals indicate that off-nadir measurements are generally suited better to retrieve τ of thin clouds.

Homogeneous freezing of supercooled droplets occurs in convective systems in low and midlatitudes. This droplet-freezing process leads to the formation of a large amount of small ice particles, so-called frozen droplets, that are transported to the upper parts of anvil outflows, where they can influence the cloud radiative properties. However, the detailed microphysics and, thus, the scattering properties of these small ice particles are highly uncertain. Here, the link between the microphysical and optical properties of frozen droplets is investigated in cloud chamber experiments, where the frozen droplets were formed, grown, and sublimated under controlled conditions. It was found that frozen droplets developed a high degree of small-scale complexity after their initial formation and subsequent growth. During sublimation, the small-scale complexity disappeared, releasing a smooth and near-spherical ice particle. Angular light scattering and depolarization measurements confirmed that these sublimating frozen droplets scattered light similar to spherical particles: that is, they had angular light-scattering properties similar to water droplets. The knowledge gained from this laboratory study was applied to two case studies of aircraft measurements in midlatitude and tropical convective systems. The in situ aircraft measurements confirmed that the microphysics of frozen droplets is dependent on the humidity conditions they are exposed to (growth or sublimation). The existence of optically spherical frozen droplets can be important for the radiative properties of detraining convective outflows.

This study presents two scientific and one operational retrieval algorithms used to obtain vertical distributions of bromine monoxide (BrO) from observations of the scattered solar light performed by the SCIAMACHY instrument in limb viewing geometry. The study begins with a discussion of the theoretical basis of all algorithms followed by an investigation of the retrieval sensitivity. Simulations with three different radiative transfer models allow us to analyze influence of the forward model implementation upon the retrieval results. By means of synthetic retrievals we analyze major sources of uncertainties in the resulting BrO profiles such as different BrO cross sections, their temperature dependence, and stratospheric aerosols. Finally, the reliability of SCIAMACHY BrO profile retrievals is demonstrated comparing results from different algorithms to each other and to balloon-borne observations.

A new "Bayesian" minimization algorithm for the retrieval of the diurnal variation of UV/vis absorbing radicals (O3, NO2, BrO, OClO and HONO) from balloon-borne limb scattered skylight observations is discussed. The method evaluates spectroscopic measurements in combination with radiative transfer calculations to drive a mathematical inversion on a discrete time and height grid. Here, the proposed method is applied to data obtained during two deployments of the mini-DOAS instrument on different balloon payloads in northern Brazil in June 2005. The retrieval is tested by comparing the inferred profiles to in-situ ozone sounding data and to measurements of the ENVISAT/SCIAMACHY satellite instrument performed during a collocated overpass. The comparison demonstrates the strength and validity of our approach. In particular for time-varying radical concentrations, photochemical corrections due to temporal mismatch of the corresponding observations are rendered dispensable. Thus, limb scanning UV/vis spectrometry from balloon platforms offers a more direct and concise approach for satellite validation of radical measurements than solar occultation measurements. Furthermore, monitoring of the diurnal variation of stratospheric radicals allows us to constrain photochemical parameters which are critical for stratospheric ozone chemistry, such as the photolysis frequency of N2O5 by observations of the diurnal variation of NO2.

Stratospheric O3 and NO2 abundances measured by different remote sensing instruments are inter-compared: (1) Line-of-sight absorptions and vertical profiles inferred from solar spectra in the ultra-violet (UV), visible and infrared (IR) wavelength ranges measured by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy) balloon payload during balloon ascent/descent and solar occultation are examined with respect to internal consistency. (2) The balloon borne stratospheric profiles of O3 and NO2 are compared to collocated space-borne skylight limb observations of the Envisat/SCIAMACHY satellite instrument. The trace gas profiles are retrieved from SCIAMACHY spectra using different algorithms developed at the Universities of Bremen and Heidelberg and at the Harvard-Smithsonian Center for Astrophysics. A comparison scheme is used that accounts for the spatial and temporal mismatch as well as differing photochemical conditions between the balloon and satellite borne measurements. It is found that the balloon borne measurements internally agree to within ±10% and ±20% for O3 and NO2, respectively, whereas the agreement with the satellite is ±20% for both gases in the 20 km to 30 km altitude range and in general worse below 20 km.

20 pags, figs13, 8 tabs, Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidising capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF (National Science Foundation) HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38%) to 0.78 (115%) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24%) to 1.25 (167%) ppt. We also use aircraft observations made during the 2011 Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) campaign, in the tropical western Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (BryVSLS). Our simulations show BryVSLS ranges from ∼4.0 to 8.0 ppt depending on the inventory. We report an optimised estimate at the lower end of this range (∼4 ppt) based on combining the CHBr3 and CH2Br2 inventories which give best agreement with the compilation of observations in the tropics. © 2013 Author(s).f 0., This work was supported by the UK Natural Environment Research Council (NERC) and the EU Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) project (SHIVA-226224-FP7-ENV-2008-1). TOMCAT work is suported by the National Centre for Atmospheric Science (NCAS). NOAA measurements were supported in part by NOAA’s Atmospheric Chemistry, Carbon Cycle and Climate Program of its Climate Program Office. Technical assistance, standardisation, and programmatic support for NOAA flask measurements was provided by C. Siso, B. Hall, and J. W. Elkins. The HIPPO project was supported by the National Science Foundation (NSF).

We carry out a case study of the transport and chemistry of bromoform and its product gases (PGs) in a sea breeze driven convective episode on 19 November 2011 along the North West coast of Borneo during the "Stratospheric ozone: Halogen Impacts in a Varying Atmosphere" (SHIVA) campaign. We use ground based, ship, aircraft and balloon sonde observations made during the campaign, and a 3-D regional online transport and chemistry model capable of resolving clouds and convection explicitly that includes detailed bromine chemistry. The model simulates the temperature, wind speed, wind direction fairly well for the most part, and adequately captures the convection location, timing, and intensity. The simulated transport of bromoform from the boundary layer up to 12 km compares well to aircraft observations to support our conclusions. The model makes several predictions regarding bromine transport from the boundary layer to the level of convective detrainment (11 to 12 km). First, the majority of bromine undergoes this transport as bromoform. Second, insoluble organic bromine carbonyl species are transported to between 11 and 12 km, but only form a small proportion of the transported bromine. Third, soluble bromine species, which include bromine organic peroxides, hydrobromic acid (HBr), and hypobromous acid (HOBr), are washed out efficiently within the core of the convective column. Fourth, insoluble inorganic bromine species (principally Br2) are not washed out of the convective column, but are also not transported to the altitude of detrainment in large quantities. We expect that Br2 will make a larger relative contribution to the total vertical transport of bromine atoms in scenarios with higher CHBr3 mixing ratios in the boundary layer, which have been observed in other regions. Finally, given the highly detailed description of the chemistry, transport and washout of bromine compounds within our simulations, we make a series of recommendations about the physical and chemical processes that should be represented in 3-D chemical transport models (CTMs) and chemistry climate models (CCMs), which are the primary theoretical means of estimating the contribution made by CHBr3 and other very short-lived substances (VSLS) to the stratospheric bromine budget.

Measurements of mixing ratio profiles of stratospheric bromine monoxide (BrO) were made using observations of BrO rotational line emission at 650.179 GHz by a balloon-borne SIS (superconductor-insulator-superconductor) submillimeterwave heterodyne limb sounder (SLS). The balloon was launched from Ft. Sumner, New Mexico (34° N) on 22 September 2011. Peak mid-day BrO abundance varied from 16 ± 2 ppt at 34 km to 6 ± 4 ppt at 16 km. Corresponding estimates of total inorganic bromine (Bry), derived from BrO vmr (volume mixing ratio) using a photochemical box model, were 21 ± 3 ppt and 11 ± 5 ppt, respectively. Inferred Bry abundance exceeds that attributable solely to decomposition of long-lived methyl bromide and other halons, and is consistent with a contribution from bromine-containing very short lived substances, BryVSLS, of 4 ppt to 8 ppt. These results for BrO and Bry were compared with, and found to be in good agreement with, those of other recent balloon-borne and satellite instruments.

A latitudinal cross-section and vertical profiles of iodine monoxide (IO) are reported from the marine boundary layer of the Western Pacific. The measurements were taken using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) during the TransBrom cruise of the German research vessel Sonne, which led from Tomakomai, Japan (42° N, 141° E) through the Western Pacific to Townsville, Australia (19° S, 146° E) in October 2009. In the marine boundary layer within the tropics (between 20° N and 5° S), IO mixing ratios ranged between 1 and 2.2 ppt, whereas in the subtropics and at mid-latitudes typical IO mixing ratios were around 1 ppt in the daytime. The profile retrieval reveals that the bulk of the IO was located in the lower part of the marine boundary layer. Photochemical simulations indicate that the organic iodine precursors observed during the cruise (CH3I, CH2I2, CH2ClI, CH2BrI) are not sufficient to explain the measured IO mixing ratios. Reasonable agreement between measured and modelled IO can only be achieved if an additional sea-air flux of inorganic iodine (e.g., I2) is assumed in the model. Our observations add further evidence to previous studies that reactive iodine is an important oxidant in the marine boundary layer.

International audience

We report on time-dependent O3, NO2 and BrO profiles measured by limb observations of scattered skylight in the stratosphere over Kiruna (67.9° N, 22.1° E) on 7 and 8 September 2009 during the autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicate that the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2, for which at T = 220 ± 5 K an overall 1.7 (+0.4 −0.2) larger ratio is found than recommended by the most recent Jet Propulsion Laboratory (JPL) compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons are likely to be (1) a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2) a smaller kBrO+NO2 at 220 K than given by Sander et al. (2011). Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This would bring estimates of Bry inferred from organic source gas measurements (e.g. CH3Br, the halons, CH2Br2, CHBr3, etc.) into closer agreement with estimates based on BrO observations (inorganic method). The consequences for stratospheric ozone due to the revised J(BrONO2)/kBrO+NO2 ratio are small (maximum −0.8%), since at high NOx (for which most Bry assessments are made) the enhanced ozone loss by overestimating Bry is compensated for by the suppressed ozone loss due to the underestimation of BrO/Bry with a smaller J(BrONO2)/kBrO+NO2 ratio.

A new climatology of stratospheric BrO profiles based on a parameterization using dynamical and chemical indicators has been developed, with the aim to apply it to the retrieval of tropospheric BrO columns from space nadir measurements. The adopted parameterization is based on three years of output data from the 3-D chemistry transport model BASCOE. The impact of the atmospheric dynamics on the stratospheric BrO distribution is treated by means of Bry/ozone correlations built from 3-D-CTM model results, while photochemical effects are taken into account using stratospheric NO2 columns as an indicator of the BrO/Bry ratio. The model simulations have been optimized for bromine chemistry and budget, and validated through comparisons using an extensive data set of ground-based, balloon-borne and satellite limb (SCIAMACHY) stratospheric BrO observations.

Validation of stratospheric BrO vertical profiles obtained by the Microwave Limb Sounder (MLS) on the Aura satellite is discussed. MLS BrO measurements are compared with expectations of its latitudinal and seasonal dependence, as well as with more localized balloon-borne measurements of BrO. We describe the expected precision and systematic errors of the version 2.2 retrieval and show that scientific studies using MLS BrO vertical profiles require extensive averaging to increase the signal-to-noise ratio to useful values. A monthly zonal mean over a 10° latitude bin (about 3,000 individual profiles) results in a precision of approximately ±4 ppt (〜25% of a typical daytime signal). Moreover, it is necessary to take day/night differences to remove large biases. The pressure range over which the data are considered useful is 10 to 3.2 hPa. Over this range, the estimated accuracy in the day/night difference is about ±20%. The vertical resolution is 5.5 km for 10 to 3.2 hPa. Day/night differences are a good measure of daytime BrO from 10 to 4.6 hPa; for 3.2 hPa the nonnegligible nighttime BrO needs to be accounted for. We infer total inorganic bromine (Bry) to be 22.1 ± 5.5 ppt on the basis of analysis of MLS measurements of BrO, which implies a contribution of 6.5 ± 5.5 ppt to stratospheric bromine from sources other than long-lived CH3Br and halons

International audience; A profiling algorithm based on the optimal estimation method is applied to ground-based zenith-sky UV-visible measurements from Harestua, Southern Norway (60° N, 11° E) in order to retrieve BrO vertical profiles. The sensitivity of the zenith-sky observations to the tropospheric BrO detection is increased by using for the spectral analysis a constant reference spectrum corresponding to clear-sky noon summer conditions. The information content and retrieval errors are characterized and it is shown that the retrieved stratospheric profiles and total columns are consistent with correlative balloon and satellite observations, respectively. Tropospheric BrO columns are derived from profiles retrieved at 80° solar zenith angle during sunrise and sunset for the 2000–2006 period. They show a marked seasonality with mean column value ranging from 1.52±0.51×1013 molec/cm2 in late winter/early spring to 0.92±0.31×1013 molec/cm2 in summer, which corresponds to 1.0±0.3 and 0.6±0.2 pptv, respectively, if we assume that BrO is uniformly mixed in the troposphere. These column values are also consistent with previous estimates made from balloon, satellite, and other ground-based observations. Daytime (10h30 local time) tropospheric BrO columns are compared to the p-TOMCAT 3-D tropospheric chemical transport model (CTM) for the 2002–2003 period. p-TOMCAT shows a good agreement with the retrieved columns except in late winter/early spring where an underestimation by the model is obtained. This feature could be explained by the non-inclusion of sea-ice bromine sources in the current version of p-TOMCAT, which can therefore not reproduce the possible transport from the polar region to Harestua of air-masses with enhanced BrO concentration due to bromine explosion events in late winter/early spring. The corresponding daytime stratospheric BrO columns are compared to the SLIMCAT 3-D stratospheric CTM. The model run used, which assumes 21.2 pptv for the Bry loading (15 pptv for long-lived bromine species + 6 extra pptv for very short-lived species (VSLS) added by a scaling of CH3Br), significantly underestimates the retrieved BrO columns. A sensitivity study shows that a good quantitative agreement can only be obtained if 8 pptv accounting for VSLS are added directly (and not by a scaling of CH3Br) to the SLIMCAT long-lived bromine species profile. This contribution of the VSLS to the total bromine loading is also consistent with recently published studies.

[1] Observations of the balloon-borne LPMA/DOAS remote sensing instruments performed in the Arctic stratosphere in February 1999 are used to constrain a photochemical model. Measurements of all relevant nitrogen, chlorine, and bromine species indicate that moderate heterogeneous chlorine activation occurred in a filament of the Arctic vortex. Model-measurement comparisons for OClO serve as an indicator of how well various scenarios of the involved reaction kinetics, in particular of the ClO-BrO and the ClO-ClO cycles, reproduce the observations. Recent suggestions for the photolysis rate of the ClO dimer, the equilibrium constant between ClO dimer and monomer, the rate of the ClO-ClO association reaction, and the branching ratio of the ClO-BrO reaction are consistent with the observations. Formation of an unstable isomer of ClONO2 cannot be reconciled with the observations. Modeled odd oxygen loss rates can be larger by 10% to 20% for the updated reaction kinetics compared to standard recommendations.

For the first time, results of four stratospheric BrO profiling instruments, are presented and compared with reference to the SLIMCAT 3-dimensional chemical transport model (3-D CTM). Model calculations are used to infer a BrO profile validation set, measured by 3 different balloon sensors, for the new Envisat/SCIAMACHY (ENVIronment SATellite/SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY) satellite instrument. The balloon observations include (a) balloon-borne in situ resonance fluorescence detection of BrO (Triple), (b) balloon-borne solar occultation DOAS measurements (Differential Optical Absorption Spectroscopy) of BrO in the UV, and (c) BrO profiling from the solar occultation SAOZ (Systeme d'Analyse par Observation Zenithale) balloon instrument. Since stratospheric BrO is subject to considerable diurnal variation and none of the measurements are performed close enough in time and space for a direct comparison, all balloon observations are considered with reference to outputs from the 3-D CTM. The referencing is performed by forward and backward air mass trajectory calculations to match the balloon with the satellite observations. The diurnal variation of BrO is considered by 1-D photochemical model calculation along the trajectories. The 1-D photochemical model is initialised with output data of the 3-D model with additional constraints on the vertical transport, the total amount and photochemistry of stratospheric bromine as given by the various balloon observations. Total [Bry]=(20.1±2.5) pptv obtained from DOAS BrO observations at mid-latitudes in 2003, serves as an upper limit of the comparison. Most of the balloon observations agree with the photochemical model predictions within their given error estimates. First retrieval exercises of BrO limb profiling from the SCIAMACHY satellite instrument on average agree to around 20% with the photochemically-corrected balloon observations of the remote sensing instruments (SAOZ and DOAS). An exception is the in situ Triple profile, in which the balloon and satellite data mostly does not agree within the given errors. In general, the satellite measurements show systematically higher values below 25 km than the balloon data and a change in profile shape above about 25 km.

Previous studies have shown that observed large O3 loss rates in cold Arctic Januaries cannot be explained with current understanding of the loss processes, recommended reaction kinetics, and standard assumptions about total stratospheric chlorine and bromine. Studies based on data collected during recent field campaigns suggest faster rates of photolysis and thermal decomposition of ClOOCl and higher stratospheric bromine concentrations than previously assumed. We show that a model accounting for these kinetic changes and higher levels of BrO can largely resolve the January Arctic O3 loss problem and closely reproduces observed Arctic O3 loss while being consistent with observed levels of ClO and ClOOCl. The model also suggests that bromine catalysed O3 loss is more important relative to chlorine catalysed loss than previously thought.

[1] Vertical profiles of stratospheric bromine monoxide (BrO) in the 15–30 km range are retrieved from SCIAMACHY limb scatter data over the globe. First validation comparisons with the balloon-borne SAOZ-BrO and LPMA/DOAS instruments indicate retrieval biases of � 20% or less. Propagated spectral fitting uncertainties lead to a precision approaching � 25% on a 2 km grid at 25 km. This worsens at higher altitudes because of reduced signal and at lower altitudes because of the reduced penetrability of the atmosphere. In terms of volume mixing ratio (VMR), the single profile precision increases from � 4 pptv at 17 km to � 8 pptv at 27 km. Repeatability, an alternative indicator of precision, is 2–3 pptv for SCIAMACHY retrievals and independent of altitude. The BrO stratospheric number density peak generally lies 5 ± 2 km above the tropopause. In the tropics, the stratospheric BrO VMR generally increases with increasing altitude. The observed stratospheric BrO global distribution is generally consistent with previous balloon measurements but does not agree well with results of a model that uses Bry inferred only from the observed breakdown of long-lived bromoalkanes (i.e., methyl bromide and halons). We find best agreement with the observed vertical and latitudinal distribution of BrO for model results that include an 8.4 ± 2 pptv contribution to stratospheric Bry, most of which is expected from the breakdown of VSL (very short lived) bromocarbons, in addition to the � 16 pptv contribution from longer-lived sources. This suggests that stratospheric Bry exceeds 20 pptv. Profiles of Bry profiles derived from the balloon measurements of BrO also suggest Bry is in excess of 20 pptv, but the uncertainty and variability of these results do not allow us to definitively rule out this concentration. We find typical BrO VMRs of � 4 pptv at 15 km in the tropical tropopause layer, suggesting that a significant portion of the bromine from VSL bromoalkane sources may be carried across the tropopause in the form of inorganic decomposition products. We discuss a variety of VSL bromocarbons species that may be contributing to the elevated concentrations of stratospheric BrO.

International audience; Within the framework of the Network for the Detection of Stratospheric Change (NDSC), an intercomparison campaign of ground-based zenith-sky viewing UV-visible spectrometers was held at the Andøya Rocket Range (69°N, 16°E) at Andenes, Norway, from February 12 to March 8, 2003. The chosen site is classified as a complementary NDSC site. Eight groups from seven countries participated in the campaign which focused on the measurements of slant columns of NO2, BrO, and OClO. This first campaign publication concentrates on measurements of the NO2 slant columns. Different analysis criteria were investigated during the campaign. These included the use of fitting parameters as chosen by each group to provide what they considered to be optimized retrievals. Additional sets of parameters, imposed for all the groups, were also used, including the wavelength interval, absorption cross sections, and species fitted. Each instrument's results were compared to the measurements of selected reference instruments, whose choice was based on a technique combining regression analysis and examination of the residuals with solar zenith angle. Considering the data obtained during the whole campaign for solar zenith angles between 75° and 95°, all instruments agreed within 5% in the case of NO2 with imposed analysis parameters in the 425–450 nm region. Measurements agree less well when retrieving the NO2 slant columns in the 400–418 nm region or when using parameters optimized by each investigator for their instrument.

On 21–22 August 2001, NO, NO2 and HNO3 mixing ratio profiles were measured at high latitudes during sunset and sunrise using the Limb Profile Monitor of the Atmosphere (LPMA) and the DOAS experiments under stratospheric balloon. Photochemical simulations using the chemistry module of the Reprobus Chemistry Transport Model (CTM) that are constrained by ozone and total NOy balloon observations reproduce well the partitioning of NOx and NOy when model results are calculated at the exact time and location of the measurement for each tangent altitude. Taking the recently recommended reaction rate coefficients for the NOy partitioning (JPL-2003) and using realistic aerosol surface area in order to initialise the model leads to an agreement between calculations and measurements better than 10% all over the covered altitude range.

International audience; Vertical profiles of ozone concentration in the high latitudes were observed by the Improved Limb Atmospheric Spectrometer (ILAS) aboard the Advanced Earth Observing Satellite (ADEOS) from November 1996 to June 1997. The ozone data obtained by the version 5.20 ILAS retrieval algorithm are compared with those obtained by the version 19 Halogen Occultation Experiment (HALOE), the version 6 Stratospheric Aerosol and Gas Experiment (SAGE) II, and the version 6 Polar Ozone and Aerosol Measurement (POAM) II retrieval algorithms. The ILAS data are also compared with ozone data measured by ozonesondes, instruments on board balloons or an aircraft, and ground-based instruments. The ILAS ozone data generally agree with its correlative data between 11 and 64 km with some exceptions. Quantitatively, the median value of the relative difference (absolute difference divided by its mean value) for these comparisons was within ±10%. Relative differences (18%) exceeding the combined measurement errors were found around 45–55 km altitude from comparisons with the HALOE and SAGE II data in January 1997 in the Southern Hemisphere (SH). Larger relative differences (around 50%) were also found below 15 km from comparisons with the HALOE and POAM II data in November 1996 in the SH, but these absolute differences were 0.10–0.16 ppmv as the median value. The ozone data processed by the version 5.20 were improved compared to the former version 3.10, which is available to the general public. The version 5.20 ozone data can be used for scientific analysis purposes based on the accuracy of the data in comparison with these other instruments.

Spectra of the atmosphere have been measured in the near-UV and visible spectral range for the first time with a Fourier transform spectrometer using direct and zenith scattered sunlight. The observations were performed in the Arctic at 79°N, 12°E in 1994. Spectra were recorded in the wavelength range 310 to 1100 nm up to a resolution of about 0.0008 nm. The use of the FT spectrometer allowed the study of atmospheric trace gas concentrations in the whole spectral region between 500 and 31,000 cm−1 (0.3–20 μm) with one instrument by only changing the beamsplitters and choosing different detectors. At a spectral resolution of 1.2 nm, the atmospheric absorptions of O3 around 505 nm and NO2 at 448 nm were analyzed. Results are compared with observations performed in the infrared with the same instrument, with TOMS data and with ozone balloon data.

The first tropospheric and stratospheric (4 to 33 km) BrO profile is presented for the inner tropics derived from balloon-borne DOAS (Differential Optical Absorption Spectroscopy) measurements. In combination with photochemical modelling, total stratospheric inorganic bromine (Bry) is deduced to be (21.5±2.5) ppt in 4.5-year-old air, probed in 2005. We derive a total contribution of (5.2±2.5) ppt from brominated very short-lived substances and inorganic product gases to stratospheric Bry Tropospheric BrO was found to be y in the lower stratosphere. Bromine source gas measurements performed 10 days earlier Laube et al., 2008, indicate a lower Bry of (17.5±0.4) ppt. Potential reasons for this discrepancy are discussed.

International audience; We have used an off-line three-dimensional (3-D) chemical transport model (CTM) to study long-term changes in stratospheric O3. The model was run from 1977–2004 and forced by ECMWF ERA-40 and operational analyses. Model runs were performed to examine the impact of increasing halogens and additional stratospheric bromine from short-lived source gases. The analyses capture much of the observed interannual variability in column ozone, but there are also unrealistic features. In particular the ERA-40 analyses cause a large positive anomaly in northern hemisphere (NH) column O3 in the late 1980s. Also, the change from ERA-40 to operational winds at the start of 2002 introduces abrupt changes in some model fields (e.g. temperature, ozone) which affect analysis of trends. The model reproduces the observed column increase in NH mid-latitudes from the mid 1990s. Analysis of a run with fixed halogens shows that this increase is not due to a significant decrease in halogen-induced loss, i.e. is not an indication of recovery. The model predicts only a small decrease in halogen-induced loss after 1999. In the upper stratosphere, despite the modelled turnover of chlorine around 1999, O3 does not increase because of the effects of increasing ECMWF temperatures, decreasing modelled CH4 at this altitude, and abrupt changes in the SH temperatures at the end of the ERA-40 period. The impact of an additional 5 pptv stratospheric bromine from short-lived species decreases mid-latitude column O3 by about 10 DU. However, the impact on the modelled relative O3 anomaly is generally small except during periods of large volcanic loading.