Abstract. It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3-4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NO x flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Global high‐precision atmospheric Δ14CO2 records covering the last two decades are presented, and evaluated in terms of changing (radio)carbon sources and sinks, using the coarse‐grid carbon cycle model GRACE. Dedicated simulations of global trends and interhemispheric differences with respect to atmospheric CO2 as well as δ13CO2 and Δ14CO2, are shown to be in good agreement with the available observations (1940–2008). While until the 1990s the decreasing trend of Δ14CO2 was governed by equilibration of the atmospheric bomb 14C perturbation with the oceans and terrestrial biosphere, the largest perturbation today are emissions of 14C‐free fossil fuel CO2. This source presently depletes global atmospheric Δ14CO2 by 12–14‰ yr−1, which is partially compensated by 14CO2 release from the biosphere, industrial 14C emissions and natural 14C production. Fossil fuel emissions also drive the changing north–south gradient, showing lower Δ14C in the northern hemisphere only since 2002. The fossil fuel‐induced north–south (and also troposphere–stratosphere) Δ14CO2 gradient today also drives the tropospheric Δ14CO2 seasonality through variations of air mass exchange between these atmospheric compartments. Neither the observed temporal trend nor the Δ14CO2 north–south gradient may constrain global fossil fuel CO2 emissions to better than 25%, due to large uncertainties in other components of the (radio)carbon cycle.

Abstract. Measurements were made of NO and NO 2, in controlled experiments to investigate their production from snow. Throughout a diurnal cycle, measurements were made of ambient air and air from inside a snowblock. Enhanced concentrations of NO and NO 2 (up to 15 pptv and 32 pptv respectively) were measured inside the snowblock. The production rate inside the block varied with intensity of incident radiation, and reached a maximum of 1.1x106 molecs/cm3/s for NO and 2.1x106 molecs/cm3/s for NO 2. A second experiment, in which the snowblock was alternately exposed to sunlight and then shaded, confirmed that the diurnal production was driven by photochemistry rather than some other diurnally varying factor. Concentrations of nitrate in the snowblock did not change as a result of 50 hours of experiments, confirming that if nitrate is the source reservoir, it can not be rapidly depleted. Snowpack production may contribute significantly to NOx concentrations in the Antarctic lower troposphere.Introduction.

Abstract. We synthesised observations of total particle number (CN) concentration from 36 sites around the world. We found that annual mean CN concentrations are typically 300-2000 cm −3 in the marine boundary layer and free troposphere (FT) and 1000-10 000 cm −3 in the continental boundary layer (BL). Many sites exhibit pronounced seasonality with summer time concentrations a factor of 2-10 greater than wintertime concentrations. We used these CN obserCorrespondence to: D. V. Spracklen (dominick@env.leeds.ac.uk) vations to evaluate primary and secondary sources of particle number in a global aerosol microphysics model. We found that emissions of primary particles can reasonably reproduce the spatial pattern of observed CN concentration (R 2 =0.46) but fail to explain the observed seasonal cycle (R 2 =0.1). The modeled CN concentration in the FT was biased low (normalised mean bias, NMB=−88%) unless a secondary source of particles was included, for example from binary homogeneous nucleation of sulfuric acid and water (NMB=−25%). Simulated CN concentrations in the continental BL were also biased low (NMB=−74%) unless the number emission of anthropogenic primary particles was increased or a Published by Copernicus Publications on behalf of the European Geosciences Union. 4776 D. V. Spracklen et al.: Explaining global aerosol number concentrations mechanism that results in particle formation in the BL was included. We ran a number of simulations where we included an empirical BL nucleation mechanism either using the activation-type mechanism (nucleation rate, J , proportional to gas-phase sulfuric acid concentration to the power one) or kinetic-type mechanism (J proportional to sulfuric acid to the power two) with a range of nucleation coefficients. We found that the seasonal CN cycle observed at continental BL sites was better simulated by BL particle formation (R 2 =0.3) than by increasing the number emission from primary anthropogenic sources (R 2 =0.18). The nucleation constants that resulted in best overall match between model and observed CN concentrations were consistent with values derived in previous studies from detailed case studies at individual sites. In our model, kinetic and activation-type nucleation parameterizations gave similar agreement with observed monthly mean CN concentrations.

In support of the first Tropospheric Ozone Assessment Report (TOAR) a relational database of global surface ozone observations has been developed and populated with hourly measurement data and enhanced metadata. A comprehensive suite of ozone data products including standard statistics, health and vegetation impact metrics, and trend information, are made available through a common data portal and a web interface. These data form the basis of the TOAR analyses focusing on human health, vegetation, and climate relevant ozone issues, which are part of this special feature.Cooperation among many data centers and individual researchers worldwide made it possible to build the world's largest collection of in-situ hourly surface ozone data covering the period from 1970 to 2015. By combining the data from almost 10,000 measurement sites around the world with global metadata information, new analyses of surface ozone have become possible, such as the first globally consistent characterisations of measurement sites as either urban or rural/remote. Exploitation of these global metadata allows for new insights into the global distribution, and seasonal and long-term changes of tropospheric ozone and they enable TOAR to perform the first, globally consistent analysis of present-day ozone concentrations and recent ozone changes with relevance to health, agriculture, and climate.Considerable effort was made to harmonize and synthesize data formats and metadata information from various networks and individual data submissions. Extensive quality control was applied to identify questionable and erroneous data, including changes in apparent instrument offsets or calibrations. Such data were excluded from TOAR data products. Limitations of a posteriori data quality assurance are discussed. As a result of the work presented here, global coverage of surface ozone data for scientific analysis has been significantly extended. Yet, large gaps remain in the surface observation network both in Schultz et al: Tropospheric Ozone Assessment Report Art. 58, page 2 of 26 terms of regions without monitoring, and in terms of regions that have monitoring programs but no public access to the data archive. Therefore future improvements to the database will require not only improved data harmonization, but also expanded data sharing and increased monitoring in data-sparse regions.