Diurnal, seasonal, and annual trends in atmospheric CO₂ at southwest London during 2000-2012:Wind sector analysis and comparison with Mace Head, Ireland

In-situ measurements of atmospheric CO have been made at Royal Holloway University of London (RHUL) in Egham (EGH), Surrey, UK from 2000 to 2012. The data were linked to the global scale using NOAA-calibrated gases. Measured CO varies on time scales that range from minutes to inter-annual and annual cycles. Seasonality and pollution episodes occur each year. Diurnal cycles vary with daylight and temperature, which influence the biological cycle of CO and the degree of vertical mixing. Anthropogenic emissions of CO dominate the variability during weekdays when transport cycles are greater than at weekends. Seasonal cycles are driven by temporal variations in biological activity and changes in combustion emissions. Maximum mole fractions (μmol/mol) (henceforth referred to by parts per million, ppm) occur in winter, with minima in late summer. The smallest seasonal amplitude observed, peak to trough, was 17.0ppm CO in 2003, whereas the largest amplitude observed was 27.1ppm CO in 2008.Meteorology can strongly modify the CO mole fractions at different time scales. Analysis of eight 45° wind sectors shows that the highest CO mole fractions were recorded from the E and SE sectors. Lowest mole fractions were observed for air masses from the S and SW. Back-trajectory and meteorological analyses of the data confirm that the dominant sources of CO are anthropogenic emissions from London and SE England. The largest annual rate of increase in the annual average of CO, 3.26ppmyr (

Diurnal, seasonal, and annual trends in tropospheric CO in Southwest London during 2000–2015: Wind sector analysis and comparisons with urban and remote sites

Ambient carbon monoxide (CO) and meteorological parameters measured at the Egham (EGH) semi-rural site in SW London during 2000–2015 have permitted wind sector analysis of diurnal and seasonal cycles, and interpretation of long-term trends. CO daily amplitudes are used as a proxy for anthropogenic emissions. At EGH, morning and evening peaks in CO arise from the dominant contribution of road transport sources. Smaller amplitudes are observed during weekends than weekdays due to lower combustion emissions, and for mornings compared to evenings due to the timing of the development and break-up of the nocturnal inversion layer or planetary boundary layer (PBL). A wavelet transform revealed that the dominant mode of CO variability is the annual cycle, with apparent winter maxima likely due to increased CO emissions from domestic heating with summer minima ascribed to enhanced dispersion and dilution during the annual maximum of PBL mixing heights. Over the last two decades, both mitigation measures to reduce CO emissions and also a major switch to diesel cars, have accompanied a change at EGH from the dominance of local diurnal sources to a site measuring close to Atlantic background levels in summer months. CO observed in the S and SW wind sectors has declined by 4.7 and 5.9 ppb yr−1 respectively. The EGH CO record shows the highest levels in the early 2000s, with levels in E and calm winds comparable to those recorded at background stations in Greater London. However, since 2012, levels in S-SW sector have become more comparable with Mace Head background except during rush-hour periods. Marked declines in CO are observed during 2000–2008 for the NE, E, SE (London) and calm wind sectors, with the smallest declines observed for the S, SW and W (background) sectors. For the majority of wind sectors, the decline in CO is less noticeable since 2008, with an apparent stabilisation for NE, E and SE after 2009. The EGH CO data record exhibits a similar but slower exponential decay, but from a much lower starting concentration, than do CO data recorded at selected monitoring sites in urban areas in SE England. CO/CO2 residuals determined using a 1 h window data in the diurnal cycle demonstrate a clear decline in CO from 2000 to 2015 during daily periods of increased vehicle traffic, which is consistent with a sustained reduction in CO emissions from the road transport sector

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

Effects of halogens on European air-quality

Halogens (Cl, Br) have a profound influence on stratospheric ozone (O3). They (Cl, Br and I) have recently also been shown to impact the troposphere, notably by reducing the mixing ratios of O3 and OH. Their potential for impacting regional air-quality is less well understood. We explore the impact of halogens on regional pollutants (focussing on O3) with the European grid of the GEOS-Chem model (0.25° × 0.3125°). It has recently been updated to include a representation of halogen chemistry. We focus on the summer of 2015 during the ICOZA campaign at the Weybourne Atmospheric Observatory on the North Sea coast of the UK. Comparisons between these observations together with those from the UK air-quality network show that the model has some skill in representing the mixing ratios/concentration of pollutants during this period. Although the model has some success in simulating the Weybourne ClNO2 observations, it significantly underestimates ClNO2 observations reported at inland locations. It also underestimates mixing ratios of IO, OIO, I2 and BrO, but this may reflect the coastal nature of these observations. Model simulations, with and without halogens, highlight the processes by which halogens can impact O3. Throughout the domain O3 mixing ratios are reduced by halogens. In northern Europe this is due to a change in the background O3 advected into the region, whereas in southern Europe this is due to local chemistry driven by Mediterranean emissions. The proportion of hourly O3 above 50 nmol mol-1 in Europe is reduced from 46% to 18% by halogens. ClNO2 from N2O5 uptake onto sea-salt leads to increases in O3 mixing ratio, but these are smaller than the decreases caused by the bromine and iodine. 12% of ethane and 16% of acetone within the boundary layer is oxidised by Cl. Aerosol response to halogens is complex with small (∼10%) reductions in PM2.5 in most locations. A lack of observational constraints coupled to large uncertainties in emissions and chemical processing of halogens make these conclusions tentative at best. However, the results here point to the potential for halogen chemistry to influence air quality policy in Europe and other parts of the world

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

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

Comparison of measured ozone production efficiencies in the marine boundary layer at two European coastal sites under different pollution regimes

Ozone production efficiencies (EN), which can be defined as the net number of ozone molecules produced per molecule of NOx oxidised, have been calculated from measurements taken during three intensive field campaigns (one in the spring, EASE 96, and two in the summer, EASE 97 and TIGER 95), at two European coastal sites (Mace Head, Ireland (EASE) and Weyboume, Norfolk (TIGER)) impacted by polluted air masses originating from both the U.K. and continental Europe, as well as relatively clean oceanic air masses from the Arctic and Atlantic. From a detailed wind sector analysis of the EASE 96 and 97 data it is clear that two general types of pollution regime were encountered at Mace Head. The calculated ozone production efficiency in clean oceanic air masses was approximately 65, which contrasted to more polluted air, from the U.K. and the continental European plume, where the efficiency decreased to between 4 and 6. The latter values of EN agree well with literature measurements conducted downwind of various urban centres in the U.S. and Europe, which are summarised in a wide-ranging review table. The EN value calculated for clean oceanic air is effectively an upper limit, owing to the relatively rapid deposition of HNO3 to the ocean. Consideration of the variation of EN With NOx for the three campaigns suggests that ozone production efficiency is relatively insensitive to both geographical location and season. The measured EN values are also compared with values derived from steady-state expressions. An observed anti-correlation between EN and measured ozone tendency is briefly discussed

Upgrading photolysis in the p-TOMCAT CTM: Model validation and assessment of the role of clouds.

A new version of the p-TOMCAT Chemical Transport Model (CTM) which includes an improved photolysis code, Fast-JX, is validated. Through offline testing we show that Fast-JX captures well the observed J(NO(2)) and J(O(1)D) values obtained at Weybourne and during a flight above the Atlantic, though with some overestimation of J(O(1)D) when comparing to the aircraft data. By comparing p-TOMCAT output of CO and ozone with measurements, we find that the inclusion of Fast-JX in the CTM strongly improves the latter's ability to capture the seasonality and levels of tracers' concentrations. A probability distribution analysis demonstrates that photolysis rates and oxidant (OH, ozone) concentrations cover a broader range of values when using Fast-JX instead of the standard photolysis scheme. This is not only driven by improvements in the seasonality of cloudiness but also even more by the better representation of cloud spatial variability. We use three different cloud treatments to study the radiative effect of clouds on the abundances of a range of tracers and find only modest effects on a global scale. This is consistent with the most relevant recent study. The new version of the validated CTM will be used for a variety of future studies examining the variability of tropospheric composition and its drivers

Influence of airmass back trajectory upon nitrogen compound composition

The speciation of nitrogen-containing compounds occurring in airmasses arriving at a site on the north Norfolk coast (UK) during 1993-1995 is examined. The data are disaggregated according to four types of back- trajectory, broadly categorised as characterising: (1) land (southern England) (2) land followed by a short stretch of shallow sea (3) the ocean (but encountering land during the last 100 km or so) and (4) the Atlantic Ocean or Arctic via the North Sea. We find clear differences in NO(y), NO(x)/NO(y), Fuchs surface area and total inorganic nitrate between the airmass types, although oxidised nitrogen speciation, i.e. nitrogen dioxide NO2, HONO, HNO3 and PAN remains broadly similar. For trajectories arriving off the land, summer samples reveal a greater degree of oxidation than those in winter. The percentage of total inorganic nitrate is enhanced and the NO(x)/NO(y) ratio appears to be suppressed in the more aged airmasses arriving over the sea. When data are disaggregated according to trajectory type, total NO(y) can be seen to relate to airmass age and clear compositional differences relating to airmass age and history appear, which are not seen in the analysis of the dataset as a whole. This suggests that the inference in some earlier published work that NO(y) composition is largely insensitive to airmass age may be incorrect if it is based on inadequate markers of airmass age. Concentrations of ammonia and ammonium are especially sensitive to back-trajectory, reflecting a strong source over the land and depletion in maritime air