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The vertical columns of formaldehyde (HCHO) retrieved from two satellite instruments, the Global Ozone Monitoring Instrument-2 (GOME-2) on Metop-A and the Ozone Monitoring Instrument (OMI) on Aura, are used to constrain global emissions of HCHO precursors from open fires, vegetation and human activities in the year 2010. To this end, the emissions are varied and optimized using the adjoint model technique in the IMAGESv2 global CTM (chemistry-transport model) on a monthly basis and at the model resolution. Given the different local overpass times of GOME-2 (09:30 LT) and OMI (13:30 LT), the simulated diurnal cycle of HCHO columns is investigated and evaluated against ground-based optical measurements at 7 sites in Europe, China and Africa. The modelled diurnal cycle exhibits large variability, reflecting competition between photochemistry and emission variations, with noon or early afternoon maxima at remote locations (oceans) and in regions dominated by anthropogenic emissions, late afternoon or evening maxima over fire scenes, and midday minima in isoprene-rich regions. The agreement between simulated and ground-based columns is found to be generally better in summer (with a clear afternoon maximum at mid-latitude sites) than in winter, and the annually averaged ratio of afternoon to morning columns is slightly higher in the model (1.126) than in the ground-based measurements (1.043). The anthropogenic VOC (volatile organic compound) sources are found to be weakly constrained by the inversions on the global scale, mainly owing to their generally minor contribution to the HCHO columns, except over strongly polluted regions, like China. The OMI-based inversion yields total flux estimates over China close to the bottom-up inventory (24.6 vs. 25.5 in the a priori) with, however, pronounced increases in the Northeast China and reductions in the south. Lower fluxes are estimated based on GOME-2 HCHO columns (20.6 TgVOC), in particular over the Northeast, likely reflecting mismatches between the observed and the modelled diurnal cycle in this region. The resulting biogenic and pyrogenic flux estimates from both optimizations generally show a good degree of consistency. A reduction of the global annual biogenic emissions of isoprene is derived, by 9 and by 13% according to GOME-2 and OMI, respectively, compared to the a priori estimate of 363 Tg in 2010. The reduction is largest (up to 25-40 %) in the Southeastern US, in accordance with earlier studies. The GOME-2 and OMI satellite columns suggest a global pyrogenic flux decrease by 36 and 33 %, respectively, compared to the GFEDv3 inventory. This decrease is especially pronounced over tropical forests such as Amazonia and Thailand/Myanmar, and is supported by comparisons with IASI CO observations. In contrast to these flux reductions, the emissions due to harvest waste burning are strongly enhanced in the Northeastern China plain in June (by ca. 70% in June according to OMI) as well as over Indochina in March. Sensitivity inversions showed robustness of the inferred estimates, which were found to lie within 7% of the standard inversion results at the global scale. [ABSTRACT FROM AUTHOR]

We present the new version (v14) of the BIRA-IASB algorithm for the retrieval of formaldehyde (H2CO) columns from spaceborne UV-Visible sensors. Applied to OMI measurements from Aura and to GOME-2 measurements from MetOp-A and B, this algorithm is used to produce global distributions of H2CO representative of mid-morning and early afternoon conditions. Its main features include (1) a new iterative DOAS scheme involving three fitting intervals to better account for the O2-O2 absorption, (2) the use of earthshine radiances averaged in the equatorial Pacific as reference spectra, (3) a destriping correction and background normalisation resolved in the along-swath position. For the air mass factor calculation, a priori vertical profiles calculated by the IMAGES chemistry transport model at 9.30 a.m. and 13.30 p.m. are used. Although the resulting GOME-2 and OMI H2CO vertical columns are found to be highly correlated, some systematic differences are observed. Afternoon columns are generally larger than morning ones, especially in mid-latitude regions. In contrast, over tropical rainforests, morning H2CO columns significantly exceed those observed in the afternoon. These differences are discussed in terms of the H2CO column variation between midmorning and early afternoon, using ground-based MAX-DOAS measurements available from seven stations in Europe, China and Africa. Validation results confirm the capacity of the combined satellite measurements to resolve diurnal variations in H2CO columns. Furthermore, vertical profiles derived from MAX-DOAS measurements in the Beijing area and in Bujumbura are used for a more detailed validation exercise. In both regions, we find an agreement better than 15% when MAX-DOAS profiles are used as a priori for the satellite retrievals. Finally regional trends in H2CO columns are estimated for the 2004-2014 period using SCIAMACHY and GOME-2 data for morning conditions, and OMI for early afternoon conditions. Consistent features are observed such as an increase of the columns in India and Central-East China, and a decrease in Eastern US and Europe. We find that the higher horizontal resolution of OMI combined to a better sampling and a more favourable illumination at mid-day allow for more significant trend estimates, especially over Europe and North America. Importantly, in some parts of the Amazonian forest, we observe with both time series a significant downward trend in H2CO columns, spatially correlated with areas affected by deforestation. [ABSTRACT FROM AUTHOR]

Daily global analyses and 5 day forecasts are generated in the context of the European Monitoring Atmospheric Composition and Climate (MACC) project using an extended version of the Integrated Forecasting System (IFS) of the European Centre for Medium-Range Weather Forecasts (ECMWF). IFS now includes modules for chemistry, deposition and emission of reactive gases, aerosols, and greenhouse gases, and the 4-dimensional variational data assimilation scheme makes use of multiple satellite observations of atmospheric composition in addition to meteorological observations. This paper describes the data assimilation setup of the new Composition-IFS (C-IFS) with respect to reactive gases and validates analysis fields of ozone (O3), carbon monoxide (CO), and nitrogen dioxide (NO2) for the year 2008 against independent observations and a control run without data assimilation. The largest improvement in CO by assimilation of MOPITT CO columns is seen in the lower troposphere of the Northern Hemisphere (NH) Extratropics during winter, and during the South African biomass burning season. The assimilation of several O3 total column and stratospheric profile retrievals greatly improves the total column, stratospheric and upper tropospheric O3 analysis fields relative to the control run. The impact on lower tropospheric ozone, which comes from the residual of the total column and stratospheric profile O3 data, is smaller, but nevertheless there is some improvement particularly in the NH during winter and spring. The impact of the assimilation of OMI tropospheric NO2 columns is small because of the short lifetime of NO2, suggesting that NO2 observations would be better used to adjust emissions instead of initial conditions. The results further indicate that the quality of the tropospheric analyses and of the stratospheric ozone analysis obtained with the C-IFS system has improved compared to the previous "coupled" model system of MACC. [ABSTRACT FROM AUTHOR]

Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of nitrous acid (HONO) and its precursor NO2 (nitrogen dioxide) have been performed daily in Beijing city center (39.98° N, 116.38° E) from July 2008 to April 2009 and at the suburban site of Xianghe (39.75° N, 116.96° E) located ∼ 60 km east of Beijing from March 2010 to December 2012. This extensive data set allowed for the first time the investigation of the seasonal cycle of HONO as well as its diurnal variation in and in the vicinity of a megacity. Our study was focused on the HONO and NO2 near-surface concentrations (0-200m layer) and total vertical column densities (VCDs) retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations. Monthly averaged HONO near-surface concentrations at local noon display a strong seasonal cycle with a maximum in late fall/winter (∼ 0.8 and 0.7 ppb at Beijing and Xianghe, respectively) and a minimum in summer (∼ 0.1 ppb at Beijing and 0.03 ppb at Xianghe). The seasonal cycles of HONO and NO2 appear to be highly correlated, with correlation coefficients in the 0.7-0.9 and 0.5-0.8 ranges at Beijing and Xianghe, respectively. The stronger correlation of HONO with NO2 and also with aerosols observed in Beijing suggests possibly larger role of NO2 conversion into HONO in the Beijing city center than at Xianghe. The observed diurnal cycle of HONO near-surface concentration shows a maximum in the early morning (about 1 ppb at both sites) likely resulting from night-time accumulation, followed by a decrease to values of about 0.1-0.4 ppb around local noon. The HONO/NO2 ratio shows a similar pattern with a maximum in the early morning (values up to 0.08) and a decrease to ∼ 0.01-0.02 around local noon. The seasonal and diurnal cycles of the HONO near-surface concentration are found to be similar in shape and in relative amplitude to the corresponding cycles of the HONO total VCD and are therefore likely mainly driven by the balance between HONO sources and the photolytic sink, whereas dilution effects appear to play only a minor role. The estimation of OH radical production from HONO and O3 photolysis based on retrieved HONO near-surface concentrations and calculated photolysis rates indicate that HONO is by far the largest source of OH radicals in winter as well as in the early morning at all seasons, while the contribution of O3 dominates in summer from mid-morning until mid-afternoon. [ABSTRACT FROM AUTHOR]

The trend in stratospheric NO2 column at the NDACC (Network for the Detection of Atmospheric Composition Change) station of Jungfraujoch (46.5° N, 8.0° E) is assessed using ground-based FTIR and zenith-scattered visible sunlight SAOZ measurements over the period 1990 to 2009 as well as a composite satellite nadir data set constructed from ERS-2/GOME, ENVISAT/SCIAMACHY, and METOP-A/GOME-2 observations over the 1996--2009 period. To calculate the trends, a linear least squares regression model including explanatory variables for a linear trend, the mean annual cycle, the quasi-biennial oscillation (QBO), solar activity, and stratospheric aerosol loading is used. For the 1990--2009 period, statistically indistinguishable trends of -3.7±1.1 %/decade and -3.6±0.9 %/decade are derived for the SAOZ and FTIR NO2 column time series, respectively. SAOZ, FTIR, and satellite nadir data sets show a similar decrease over the 1996--2009 period, with trends of -2.4±1.1 %/decade, -4.3±1.4 %/decade, and -3.6±2.2 %/decade, respectively. The fact that these declines are opposite in sign to the globally observed +2.5%/decade trend in N2O, suggests that factors other than N2O are driving the evolution of stratospheric NO2 at northern mid-latitudes. Possible causes of the decrease in stratospheric NO2 columns have been investigated. The most likely cause is a change in the NO2/NO partitioning in favor of NO, due to a possible stratospheric cooling and a decrease in stratospheric chlorine content, the latter being further confirmed by the negative trend in the ClONO2 column derived from FTIR observations at Jungfraujoch. Decreasing ClO concentrations slows the NO+ClO ! NO2 +Cl reaction and a stratospheric cooling slows the NO+O3→NO2 +O2 reaction, leaving more NOx in the form of NO. The slightly positive trends in ozone estimated from ground- and satellite-based data sets are also consistent with the decrease of NO2 through the NO2 +O3→NO3 +O2 reaction. Finally, we cannot rule out the possibility that a strengthening of the Dobson-Brewer circulation, which reduces the time available for N2O photolysis in the stratosphere, could also contribute to the observed decline in stratospheric NO2 above Jungfraujoch. [ABSTRACT FROM AUTHOR]

Formaldehyde (HCHO) columns have been retrieved from ground-based Fourier transform infrared (FTIR) campaign measurements in 2004 and 2007 and from UV-Visible MAX-DOAS measurements in 2004-2005 at the NDACC site of Réunion Island (21°S, 55°E). The FTIR and MAX-DOAS daily mean formaldehyde total columns are intercompared in their common measurement period, from August to October 2004. The ground-based data are also compared to correlative SCIAMACHY data. The comparisons account for the vertical sensitivity differences of the data sets, by including their respective averaging kernels. Complete error budgets are also presented. The FTIR and MAX-DOAS daily mean total columns agree very well: no significant bias is observed and the standard deviation of the comparisons is only 8%. Both FTIR and MAX-DOAS HCHO total columns are in good agreement with SCIAMACHY values in the 2004-2005 period, with standard deviations of 21% and 31%, respectively. The same seasonal cycle is observed by the different instruments, with a minimum in austral winter and a maximum in February-March. The FTIR and MAX-DOAS data are confronted with HCHO columns calculated by a global CTM, the IMAGES model. The model underestimates the HCHO columns by 23-29% in comparison with FTIR, and by 15% in comparison with DOAS. This bias might have multiple causes, including an underestimation of OH concentrations in the model (as indicated by a sensitivity study using prescribed OH fields) and/or an underestimated contribution of large-scale transport of HCHO precursors from Madagascar. The latter hypothesis is comforted by the large observed day-to-day variability of HCHO columns, and by the observation that the peak values of FTIR columns can often be associated with free tropospheric transport patterns from source regions over Madagascar to Réunion Island, according to simulations performed with the Lagrangian particle dispersion model FLEXPART. [ABSTRACT FROM AUTHOR]

The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument was launched aboard the environmental satellite ENVISAT into its sun-synchronous orbit on 1 March 2002. The short-lived species NO2 is one of the key target products of MIPAS that are operationally retrieved from limb emission spectra measured in the stratosphere and mesosphere. Within the MIPAS validation activities, a large number of independent observations from balloons, satellites and ground-based stations have been compared to European Space Agency (ESA) version 4.61 operational NO2 data comprising the time period from July 2002 until March 2004 where MIPAS measured with full spectral resolution. Comparisons between MIPAS and balloon-borne observations carried out in 2002 and 2003 in the Arctic, at mid-latitudes, and in the tropics show a very good agreement below 40 km altitude with a mean deviation of roughly 3%, virtually without any significant bias. The comparison to ACE satellite observations exhibits only a small negative bias of MIPAS which appears not to be significant. The independent satellite instruments HALOE, SAGE II, and POAM III confirm in common for the spring-summer time period a negative bias of MIPAS in the Arctic and a positive bias in the Antarctic middle and upper stratosphere exceeding frequently the combined systematic error limits. In contrast to the ESA operational processor, the IMK/IAA retrieval code allows accurate inference of NO2 volume mixing ratios under consideration of all important non-LTE processes. Large differences between both retrieval results appear especially at higher altitudes, above about 50 to 55 km. These differences might be explained at least partly by non-LTE under polar winter conditions but not at mid-latitudes. Below this altitude region mean differences between both processors remain within 5% (during night) and up to 10% (during day) under undisturbed (September 2002) conditions and up to 40% under perturbed polar night conditions (February and March 2004). The intercomparison of ground-based NDACC observations shows no significant bias between the FTIR measurements in Kiruna (68° N) and MIPAS in summer 2003 but larger deviations in autumn and winter. The mean deviation over the whole comparison period remains within 10%. A mean negative bias of 15% for MIPAS daytime and 8% for nighttime observations has been determined for UV-vis comparisons over Harestua (60° N). Results of a pole-to-pole comparison of ground-based DOAS/UV-visible sunrise and MIPAS mid-morning column data has shown that the mean agreement in 2003 falls within the accuracy limit of the comparison method. Altogether, it can be indicated that MIPAS NO2 profiles yield valuable information on the vertical distribution of NO2 in the lower and middle stratosphere (below about 45 km) during day and night with an overall accuracy of about 10-20% and a precision of typically 5-15% such that the data are useful for scientific studies. In cases where extremely high NO2 occurs in the mesosphere (polar winter) retrieval results in the lower and middle stratosphere are less accurate than under undisturbed atmospheric conditions. [ABSTRACT FROM AUTHOR]

For the first time, results of all four existing 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, (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±2.8) 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 agree to <±50% with the photochemically-corrected balloon observations, and tend to show less agreement below 20 km. [ABSTRACT FROM AUTHOR]

We present the results of an intercomparison exercise between six different radiative transfer (RT) models carried out in the framework of QUILT, an EU funded project based on the exploitation of the Network for the Detection of Stratospheric Change (NDSC). RT modeling is an important step in the interpretation of Differential Optical Absorption Spectroscopy (DOAS) observations. It allows the conversion of the slant column densities (SCDs) into vertical column densities (VCDs) using calculated air mass factors (AMFs). The originality of our study resides in comparing SCD simulations in multi-axis (MAX) geometry (trace gases: NO2 and HCHO) and in taking into account the photochemical enhancement for calculating SCDs of rapidly photolysing species (BrO, NO2 and OClO) in zenith-sky geometry. Concerning the MAX simulations, good agreement is observed between the different models with the calculated NO2 and HCHO SCDs differing by no more than 5% in the elevation and solar zenith angles (SZA) ranges investigated (5°-20° and 35°-85°, respectively). The impacts of aerosol scattering, ground albedo, and relative azimuth on MAX simulations have also been tested. Large discrepancies appear for the aerosol effect, suggesting differences between models in the treatment of the aerosol scattering. A better agreement is obtained in the case of the ground albedo and relative azimuth effects. In zenith-sky geometry, the different models agree generally well, especially below 90° SZA. At higher SZA, larger discrepancies are observed with relative difference values between 2% and 14% in some cases. All the initialization data and results have been made publicly available through the QUILT project web site (http://nadir.nilu.no/quilt/), enabling the testing of other RT codes designed for the calculation of SCDs/AMFs. [ABSTRACT FROM AUTHOR]