Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is approximately 50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

[1] The first global simultaneous observations of glyoxal (CHOCHO) and formaldehyde (HCHO) columns retrieved from measurements by the Scanning Imaging Absorption Spectrometer for Atmospheric Cartography (SCIAMACHY) satellite instrument are presented and compared to model calculations. The global pattern of the distribution of CHOCHO is similar to that of HCHO. High values are observed over areas with large biogenic isoprene emissions (Central Africa, parts of South America, and Indonesia). Also regions with biomass burning and anthropogenic pollution exhibit elevated levels of CHOCHO. The ratio of the columns of CHOCHO to HCHO is generally of the order of 0.05 in regions having biogenic emissions, which is in reasonable agreement with the current understanding of the oxidation of hydrocarbons emitted by the biosphere. However and in contrast to our model, high values of both HCHO and CHOCHO are also observed over areas of the tropical oceans. This is tentatively attributed to outflow from the continents and local oceanic biogenic sources of the precursors of HCHO and CHOCHO.

Abstract.A new approach to derive tropospheric concentrations of some atmospheric trace gases from ground-based UV/vis measurements is described. The instrument, referred to as the MAX-DOAS, is based on the well-known UV/vis instruments, which use the sunlight scattered in the zenith sky as the light source and the method of Differential Optical Absorption Spectroscopy (DOAS) to derive column amounts of absorbers like ozone and nitrogen dioxide. Substantial enhancements have been applied to this standard setup to use different lines of sight near to the horizon as additional light sources (MAX -multi axis). Results from measurements at Ny-Ålesund (79 • N, 12 • E) are presented and interpreted with the full-spherical radiative transfer model SCIATRAN. In particular, measurements of the oxygen dimer O 4 which has a known column and vertical distribution in the atmosphere are used to evaluate the sensitivity of the retrieval to parameters such as multiple scattering, solar azimuth, surface albedo and refraction in the atmosphere and also to validate the radiative transfer model. As a first application, measurements of NO 2 emissions from a ship lying in Ny-Ålesund harbour are presented. The results of this study demonstrate the feasibility of long term UV/vis multi axis measurement that can be used to derive not only column amounts of different trace gases but also some information on the vertical location of these absorbers.

Although tropospheric reactive halogen chemistry is well studied in coastal and polar environments, the presence of halogens over the open ocean environment has not been widely reported. The impacts of halogens on the tropical open ocean marine boundary layer (MBL), in particular, are not well characterised. This paper describes observations of iodine monoxide (IO) and bromine oxide (BrO) over eight months in the tropical open ocean MBL, on the north-eastern side of São Vicente (Cape Verde Islands, 16.85° N, 24.87° W). The highest BrO mixing ratio observed was 5.6±1 pmol mol⁻¹, while the maximum observed IO mixing ratio was 3.1±0.4 pmol mol⁻¹. The average values seen between 09:00–17:00 GMT were ~2.8 pmol mol⁻¹ for BrO and ~1.5 pmol mol⁻¹ for IO; these averages showed little variability over the entire campaign from November 2006 to June 2007. A 1-dimensional chemistry and transport model is used to study the evolution of iodine species and quantify the combined impact of iodine and bromine chemistry on the oxidising capacity of the MBL. It appears that the measured fluxes of iodocarbons are insufficient to account for the observed levels of IO, and that an additional I atom source is required, possibly caused by the deposition of O₃ onto the ocean surface in the presence of solar radiation. Modelling results also show that the O₃ depletion observed at Cape Verde cannot be explained in the absence of halogen chemistry, which contributes ~45% of the observed O₃ depletion at the height of measurements (10 m) during summer. The model also predicts that halogens decrease the hydroperoxy radical (HO₂) concentration by ~14% and increase the hydroxyl radical (OH) concentration by ~13% near the ocean surface. The oxidation of dimethyl sulphide (DMS) by BrO takes place at a comparable rate to oxidation by OH in this environment. Finally, the potential of iodine chemistry to form new particles is explored and conditions under which particle formation could be important in the remote MBL are discussed

The performance of a proton exchange membrane fuel cell (PEMFC) was evaluated at 80°C in H2 with defined amounts of CO (25 to 250 ppm) and pure oxygen. Membrane electrode assemblies (MEAs) were made using Nafion™ 117 with carbon‐supported dispersed Pt, Pt0.7Ru0.3 , and Pt0.5Ru0.5 as anode catalysts, and Pt as a cathode catalyst. For comparison the MEAs were first characterized in H2//O2 . In H2/CO//O2 steady‐state current‐voltage curves were obtained after a poisoning period. It was found that the performance of the cell depends strongly on the CO concentration and the anode catalyst used. For Pt0.5Ru0.5 as anode catalyst, the maximum power density in H2/CO//O2 was enhanced by a factor of four compared with a Pt anode catalyst. Using Pt0.5Ru0.5 no difference in power density was found between pure H2 and H2 /100 ppm CO up to current densities of about 0.4Acm−2 .

Abstract. New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale. In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute > 20% of glyoxal-SOA mass, and the total mass formed (5.8% of total SOA in the LA basin) is about a third of the simple uptake coefficient formulation without consideration of aerosol phase state and composition. Results from the continental US simulation reveal the much larger potential to form glyoxal-SOA over the eastern continental US. Interestingly, the low concentrations of glyoxal-SOA over the western continental US are not due to the lack of a potential to form glyoxal-SOA here. Rather these small glyoxal-SOA concentrations reflect dry conditions and high salt concentrations, and the potential to form SOA mass here will strongly depend on the water associated with particles.

Abstract. Fluorescence Assay by Gas Expansion (FAGE) has been used to detect ambient levels of OH and HO2 radicals at the Cape Verde Atmospheric Observatory, located in the tropical Atlantic marine boundary layer, during May and June 2007. Midday radical concentrations were high, with maximum concentrations of 9 ×106 molecule cm−3 and 6×108 molecule cm−3 observed for OH and HO2, respectively. A box model incorporating the detailed Master Chemical Mechanism, extended to include halogen chemistry, heterogeneous loss processes and constrained by all available measurements including halogen and nitrogen oxides, has been used to assess the chemical and physical parameters controlling the radical chemistry. The model was able to reproduce the daytime radical concentrations to within the 1 σ measurement uncertainty of 20% during the latter half of the measurement period but significantly under-predicted [HO2] by 39% during the first half of the project. Sensitivity analyses demonstrate that elevated [HCHO] (~2 ppbv) on specific days during the early part of the project, which were much greater than the mean [HCHO] (328 pptv) used to constrain the model, could account for a large portion of the discrepancy between modelled and measured [HO2] at this time. IO and BrO, although present only at a few pptv, constituted ~19% of the instantaneous sinks for HO2, whilst aerosol uptake and surface deposition to the ocean accounted for a further 23% of the HO2 loss at noon. Photolysis of HOI and HOBr accounted for ~13% of the instantaneous OH formation. Taking into account that halogen oxides increase the oxidation of NOx (NO → NO2), and in turn reduce the rate of formation of OH from the reaction of HO2 with NO, OH concentrations were estimated to be 9% higher overall due to the presence of halogens. The increase in modelled OH from halogen chemistry gives an estimated 9% shorter lifetime for methane in this region, and the inclusion of halogen chemistry is necessary to model the observed daily cycle of O3 destruction that is observed at the surface. Due to surface losses, we hypothesise that HO2 concentrations increase with height and therefore contribute a larger fraction of the O3 destruction than at the surface.

[1] Iodine chemistry in the marine boundary layer has attracted increasing attention over the last few years because iodine oxides cause ozone destruction, change the atmospheric oxidising capacity, and can form ultrafine particles. However, the chemistry of iodine in polluted environments is not well understood: its effects are assumed to be inhibited by reactions involving NO x (NO 2 & NO). This paper describes Differential Optical Absorption Spectroscopy (DOAS) observations of iodine species (I 2 , OIO and IO) and the nitrate radical (NO 3 ) at a semi-polluted coastal site in Roscoff, France. Significant concentrations of IO and I 2 were measured during daytime, indicating efficient recycling of iodine from iodine nitrate (IONO 2 ). I 2 , IO, OIO and NO 3 were observed at night. These observations are interpreted using a one dimensional model to demonstrate that iodine plays an important role even in polluted environments due to recycling mechanisms not considered previously.