The multi-seasonal NO_y budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign

International audienceMeasurements of individual NOy components were carried out at Halley station in coastal Antarctica. The measurements were made as part of the CHABLIS campaign (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) and cover over half a year, from austral winter 2004 through to austral summer 2005. They are the longest duration and most extensive NOy budget study carried out to date in polar regions. Results show clear dominance of organic NOy compounds (PAN and MeONO2) during the winter months, with low concentrations of inorganic NOy, but a reversal of this situation towards summer when the balance shifts in favour of inorganic NOy. Multi-seasonal measurements of surface snow nitrate correlate strongly with inorganic NOy species. One case study in August suggested that particulate nitrate was the dominant source of nitrate to the snowpack, but this was not the consistent picture throughout the measurement period. An analysis of NOx production rates showed that emissions of NOx from the snowpack dominate over gas-phase sources of "new NOx", suggesting that, for certain periods in the past, the flux of NOx into the boundary layer can be calculated from ice core nitrate data

Radial Diffusion and Penetration of Gas Molecules and Aerosol Particles through Laminar Flow Reactors, Denuders, and Sampling Tubes

Flow reactors, denuders, and sampling tubes are essential tools for many applications in analytical and physical chemistry and engineering. We derive a new method for determining radial diffusion effects and the penetration or transmission of gas molecules and aerosol particles through cylindrical tubes under laminar flow conditions using explicit analytical equations. In contrast to the traditional Brown method [Brown, R. L. J. Res. Natl. Bur. Stand. (U. S.) 1978, 83, 1-8] and CKD method (Cooney, D. O.; Kim, S. S.; Davis, E. J. Chem. Eng. Sci. 1974, 29, 1731-1738), the new approximation developed in this study (known as the KPS method) does not require interpolation or numerical techniques. The KPS method agrees well with the CKD method under all experimental conditions and also with the Brown method at low Sherwood numbers. At high Sherwood numbers corresponding to high uptake on the wall, flow entry effects become relevant and are considered in the KPS and CKD methods but not in the Brown method. The practical applicability of the KPS method is demonstrated by analysis of measurement data from experimental studies of rapid OH, intermediate NO3, and slow O3 uptake on various organic substrates. The KPS method also allows determination of the penetration of aerosol particles through a tube, using a single equation to cover both the limiting cases of high and low deposition described by Gormley and Kennedy ( Proc. R. Ir. Acad., Sect. A. 1949, 52A, 163-169). We demonstrate that the treatment of gas and particle diffusion converges in the KPS method, thus facilitating prediction of diffusional loss and penetration of gases and particles, analysis of chemical kinetics data, and design of fluid reactors, denuders, and sampling lines

Methods, fluxes and sources of gas phase alkyl nitrates in the coastal air

The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3-C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO2 levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor. © 2014 Springer International Publishing Switzerland

Measurement techniques in gas-phase tropospheric chemistry: a selective view of the past, present, and future

Measurements of trace gases and photolysis rates in the troposphere are essential for understanding photochemical smog and global environmental change. Chemical measurement techniques have progressed enormously since the first regular observations of tropospheric ozone in the 19th century. In contrast, by the 1940s spectroscopic measurements were already of a quality that would have allowed the use of modern analysis techniques to reduce interference between gases, although such techniques were not applied at the time. Today, chemical and spectroscopic techniques complement each other on a wide range of platforms. The boundaries between spectroscopic techniques will retreat as more Fourier transform spectrometers are used at visible wavelengths and as wide-band lidars are extended, and combining chemical techniques will allow detection of more trace gases with better sensitivity. Other future developments will focus on smaller, lighter instruments to take advantage of new platforms such as unmanned aircraft and to improve the effectiveness of urban sampling

Ozone and other secondary photochemical pollutants: Chemical processes governing their formation in the planetary boundary layer

The chemical processing of pollutants emitted into the atmosphere leads to a variety of oxidised products, which are commonly referred to as secondary pollutants. Such pollutants are often formed on local or regional scales in the planetary boundary layer, and may have direct health impacts and/or play wider roles in global atmospheric chemistry. In the present review, a comparatively detailed description of our current understanding of the chemical mechanisms leading to the generation of secondary pollutants in the troposphere is provided, with particular emphasis on chemical processes occurring in the planetary boundary layer. Much of the review is devoted to a discussion of the gas-phase photochemical transformations of nitrogen oxides (NOx) and volatile organic compounds (VOCs), and their role in the formation of ozone (O-3) The chemistry producing a variety of other oxidants and secondary pollutants (e.g., organic oxygenates; oxidised organic and inorganic nitrogen compounds), which are often formed in conjunction with O-3, is also described. Some discussion of nighttime chemistry and the formation of secondary organic aerosols (SOA) in tropospheric chemistry is also given, since these are closely linked to the gas-phase photochemical processes. In many cases, the discussion of the relative importance of the various processes is illustrated by observational data, with emphasis generally placed on conditions appropriate to the UK and northwest continental Europe. (C) 2000 Elsevier Science Ltd. All rights reserved

Observed trends in ground-level O₃ in Monterrey, Mexico, during 1993–2014: comparison with Mexico City and Guadalajara

Here, we present an assessment of long-term trends in O3 and odd oxygen (O3 + NO2) at the industrial Monterrey metropolitan area (MMA) in NE Mexico. Diurnal amplitudes in Ox (AVd) are used as a proxy for net O3 production, which is influenced by the NO2 photolysis rate. No significant differences in the AVd are observed between weekends and weekdays, although the largest AVd values are observed at sites downwind of industrial areas. The highest O3 mixing ratios are observed in spring, with minimum values in winter. The largest annual variations in O3 are typically observed downwind of the MMA, with the lowest variations generally recorded in highly populated areas and close to industrial areas. A wind sector analysis of mixing ratios of O3 precursors revealed that the dominant sources of emissions are located in the industrial regions within the MMA and surrounding area. Significant increasing trends in O3 in spring, summer, and autumn are observed depending on site location, with trends in annual averages ranging between 0.19 and 0.33 ppb yr−1. Overall, from 1993 to 2014, within the MMA, O3 has increased at an average rate of 0.22 ppb yr−1 (p < 0. 01), which is in marked contrast with the decline of 1.15 ppb yr−1 (p < 0. 001) observed in the Mexico City metropolitan area (MCMA) for the same period. No clear trend is observed from 1996 to 2014 within the Guadalajara metropolitan area (GMA)