F. Hendrick

Comparison of measurements and model calculations of stratospheric bromine monoxide

Ground-based zenith sky UV-visible measurements of stratospheric bromine monoxide (BrO) slant column densities are compared with simulations from the SLIMCAT three-dimensional chemical transport model. The observations have been obtained from a network of 11 sites, covering high and midlatitudes of both hemispheres. This data set gives for the first time a near-global picture of the distribution of stratospheric BrO from ground-based observations and is used to test our current understanding of stratospheric bromine chemistry. In order to allow a direct comparison between observations and model calculations, a radiative transfer model has been coupled to the chemical model to calculate simulated slant column densities. The model reproduces the observations in general very well. The absolute amount of the BrO slant columns is consistent with a total stratospheric bromine loading of 20 ± 4 ppt for the period 1998-2000, in agreement with previous estimates. The seasonal and latitudinal variations of BrO are well reproduced by the model. In particular, the good agreement between the observed and modeled diurnal variation provides strong evidence that the BrO-related bromine chemistry is correctly modeled. A discrepancy between observed and modeled BrO at high latitudes during events of chlorine activation can be resolved by increasing the rate constant for the reaction BrO + ClO → BrCl + O 2 to the upper limit of current recommendations. However, other possible causes of the discrepancy at high latitudes cannot be ruled out.

Sulfur dioxide vertical column DOAS retrievals from the Ozone Monitoring Instrument: Global observations and comparison to ground-based and satellite data

We present a new data set of sulfur dioxide (SO2) vertical columns from observations of the Ozone Monitoring Instrument (OMI)/AURA instrument between 2004 and 2013. The retrieval algorithm used is an advanced Differential Optical Absorption Spectroscopy (DOAS) scheme combined with radiative transfer calculation. It is developed in preparation for the operational processing of SO2 data product for the upcoming TROPOspheric Monitoring Instrument/Sentinel 5 Precursor mission. We evaluate the SO2 column results with those inferred from other satellite retrievals such as Infrared Atmospheric Sounding Interferometer and OMI (Linear Fit and Principal Component Analysis algorithms). A general good agreement between the different data sets is found for both volcanic and anthropogenic SO2 emission scenarios. We show that our algorithm produces SO2 columns with low noise and is able to provide accurate estimates of SO2. This conclusion is supported by important validation results over the heavily polluted site of Xianghe (China). Nearly 4 years of OMI and ground-based multiaxis DOAS SO2 columns are compared, and an excellent match is found. We also highlight the improved performance of the algorithm in capturing weak SO2 sources by detecting shipping SO2 emissions in long-term averaged data, an unreported measurement from space.

Odin/OSIRIS observations of stratospheric BrO: Retrieval methodology, climatology, and inferred Bry

A 7+ year (2001–2008) data set of stratospheric BrO profiles measured by the Optical Spectrograph and Infra-Red Imager System (OSIRIS) instrument, a UV-visible spectrometer measuring limb-scattered sunlight from the Odin satellite, is presented. Zonal mean radiance spectra are computed for each day and inverted to yield effective daily zonal mean BrO profiles from 16 to 36 km. A detailed description of the retrieval methodology and error analysis is presented. Single-profile precision and effective resolution are found to be about 30% and 3–5 km, respectively, throughout much of the retrieval range. Individual profile and monthly mean comparisons with ground-based, balloon, and satellite instruments are found to agree to about 30%. A BrO climatology is presented, and its morphology and correlation with NO2 is consistent with our current understanding of bromine chemistry. Monthly mean Bry maps are derived. Two methods of calculating total Bry in the stratosphere are used and suggest (21.0 ± 5.0) pptv with a contribution from very short lived substances of (5.0 ± 5.0) pptv, consistent with other recent estimates.

First satellite detection of volcanic OClO after the eruption of Puyehue-Cordon Caulle

Volcanoes release large amounts of halogen species such as HCl and HBr, which can be converted into reactive halogens by heterogeneous photochemical reactions that are currently not fully characterized. Here we report on the first satellite detection of volcanic chlorine dioxide (OClO). Measurements were performed using the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography instrument for the ash-laden plume emitted after the 2011 eruption of Puyehue-Cordon Caulle in Chile. We also identified volcanic BrO using the Ozone Monitoring Instrument, as well as enhanced HCl in data of the Microwave Limb Sounder instrument. These observations suggest that OClO was formed in the plume by the ClO + BrO reaction in presence of a large excess of ClO. The present satellite data set could help better understand reactive halogen chemistry in volcanic plumes and its impact on atmospheric composition.

One-decade trend analysis of stratospheric BrO over Harestua (60°N) and Lauder (45°S) reveals a decline

A trend analysis is performed of stratospheric BrO from ground-based UV-visible observations at Harestua (60°N, 11°E) and Lauder (45°S, 170°E) from 1995 through 2005. At both stations, a positive trend of about +2.5% per year is found for the 1995-2001 period, while a negative trend of about -1% per year is obtained between 2001 and 2005. Given a mean age of air of about 4 ± 1 years, the decline in stratospheric bromine since 2002 follows the decline of tropospheric organic bromine observed since the second half of 1998, as a result of the Montreal Protocol. These findings confirm that the impact of the Montreal Protocol restrictions on brominated substances have now reached the stratosphere. From our study, we have also derived a contribution of 6 ± 4 ppt of the brominated very short-lived substances and inorganic bromine tropospheric sources to the total bromine loading.

Measurements of Tropospheric NO2 in Romania Using a Zenith-Sky Mobile DOAS System and Comparisons with Satellite Observations

In this paper we present a new method for retrieving tropospheric NO2 Vertical Column Density (VCD) from zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements using mobile observations. This method was used during three days in the summer of 2011 in Romania, being to our knowledge the first mobile DOAS measurements peformed in this country. The measurements were carried out over large and different areas using a mobile DOAS system installed in a car. We present here a step-by-step retrieval of tropospheric VCD using complementary observations from ground and space which take into account the stratospheric contribution, which is a step forward compared to other similar studies. The detailed error budget indicates that the typical uncertainty on the retrieved NO2tropospheric VCD is less than 25%. The resulting ground-based data set is compared to satellite measurements from the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment-2 (GOME-2). For instance, on 18 July 2011, in an industrial area located at 47.03°N, 22.45°E, GOME-2 observes a tropospheric VCD value of (3.4 ± 1.9) × 1015 molec./cm2, while average mobile measurements in the same area give a value of (3.4 ± 0.7) × 1015 molec./cm2. On 22 August 2011, around Ploiesti city (44.99°N, 26.1°E), the tropospheric VCD observed by satellites is (3.3 ± 1.9) × 1015 molec./cm2 (GOME-2) and (3.2 ± 3.2) × 1015 molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 1015 molec./cm2. Average ground measurements over “clean areas”, on 18 July 2011, give (2.5 ± 0.6) × 1015 molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 1015 molec./cm2.

Comparison of tropospheric NO 2 columns from MAX-DOAS retrievals and regional air quality model simulations

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) tropospheric NO2 column retrievals from four European measurement stations are compared to simulations from five regional air quality models which contribute to the European regional ensemble forecasts and reanalyses of the operational Copernicus Atmosphere Monitoring Service (CAMS). Compared to other observational data usually applied for regional model evaluation, MAX-DOAS data are closer to the regional model data in terms of horizontal and vertical resolution, and multiple measurements are available during daylight, so that, for example, diurnal cycles of trace gases can be investigated. In general, there is good agreement between simulated and retrieved NO2 column values for individual MAX-DOAS measurements with correlations between 35 % and 70 % for individual models and 45 % to 75 % for the ensemble median for tropospheric NO2 vertical column densities (VCDs), indicating that emissions, transport and tropospheric chemistry of NOx are on average well simulated. However, large differences are found for individual pollution plumes observed by MAX-DOAS. Most of the models overestimate seasonal cycles for the majority of MAX-DOAS sites investigated. At the urban stations, weekly cycles are reproduced well, but the decrease towards the weekend is underestimated and diurnal cycles are overall not well represented. In particular, simulated morning rush hour peaks are not confirmed by MAX-DOAS retrievals, and models fail to reproduce observed changes in diurnal cycles for weekdays versus weekends. The results of this study show that future model development needs to concentrate on improving representation of diurnal cycles and associated temporal scalings. Published by Copernicus Publications on behalf of the European Geosciences Union. 2796 A.-M. Blechschmidt et al.: Comparison of NO2 columns from MAX-DOAS and regional air quality models

Link Between Arctic Tropospheric BrO Explosion Observed From Space and Sea‐Salt Aerosols From Blowing Snow Investigated Using Ozone Monitoring Instrument BrO Data and GEOS‐5 Data Assimilation System

Bromine radicals (Br + BrO) are important atmospheric species owing to their ability to catalytically destroy ozone as well as their potential impacts on the oxidative pathways of many trace gases, including dimethylsulfide and mercury. Using space‐based observations of BrO, recent studies have reported rapid enhancements of tropospheric BrO over large areas (so called “BrO explosions”) connected to near‐surface ozone depletion occurring in polar spring. However, the source(s) of reactive bromine and mechanism(s) that initiate these BrO explosions are uncertain. In this study, we investigate the relationships between Arctic BrO explosions and two of the proposed sources of reactive bromine: sea‐salt aerosol (SSA) generated from blowing snow and first‐year (seasonal) sea ice. We use tropospheric column BrO derived from the Ozone Monitoring Instrument (OMI) in conjunction with the Goddard Earth Observing System Version 5 (GEOS‐5) data assimilation system provided by National Aeronautics and Space Administration Global Modeling and Assimilation Office. Case studies demonstrate a strong association between the temporal and spatial extent of OMI‐observed BrO explosions and the GEOS‐5 simulated blowing snow‐generated SSA during Arctic spring. Furthermore, the frequency of BrO explosion events observed over the 11‐year record of OMI exhibits significant correlation with a time series of the simulated SSA emission flux in the Arctic and little to no correlation with a time series of satellite‐based first‐year sea ice area. Therefore, we conclude that SSA generated by blowing snow is an important factor in the formation of the BrO explosion observed from space during Arctic spring.

Re-examine the APEC blue in Beijing 2014

APEC blue was coined to describe the impact of short-term curbs on air pollution during the Asian-Pacific Economic Cooperation (APEC) Summit organized in Beijing in November 2014 and has been a hot topic among both general public and scientific sector in China. The consensus that gaseous agents NO2 and SO2 are greatly reduced in response to the control and restriction strategies implemented during the Summit period is shared by earlier literature. However, the re-examination of APEC blue conducted in the present study comes to a more contrasted conclusion. The remarkable drop in NO2 abundances is confirmed in terms of both surface concentration and vertical column, whereas corresponding SO2 changes are found to be marginal and not statistically significant, indicating that the decline of SO2 was more tied to natural or random variability rather than externally forced. To explain the contrasted responses of NO2 and SO2 during the APEC summit, short-term variations of these species are further placed in the context of a longer term perspective, which reveals a striking contrast in the pathways of the secular tendency in NO2 and SO2 emissions and corresponding measured abundances of both pollutants. On the one hand, NO2 emissions exhibit a sharp rise by 30–50% from 2006-2010 to 2011–2014; on the other hand, SO2 emissions have undergone a gradual decrease in the last decade and have currently returned to their pre-2000 level. Therefore, short-term control measures are expected to be more effective in reducing the levels of NO2 than SO2.

Maximizing Degrees of Freedom in MAX-DOAS Retrievals of BrO from Remote Tropical Marine Mountaintops

We are developing sensitive atmospheric vertical profile retrieval capabilities from MAX-DOAS sensors on tropical island mountaintops. Particularly, we target BrO which has significant impacts on the lifetime of greenhouse gases such as O3 and CH4.