Wlodek Zahorowski

Chemical characterization of the boundary layer outflow of air pollution to Hong Kong during February–April 2001

[1] As a cooperative effort with the TRACE-P and ACE-Asia intensive in the spring of 2001, trace gases and aerosols were measured at a relatively remote coastal site (Hok Tsui) in southeastern Hong Kong. The main objective of the measurement program was to provide continuous ground-based data in the subtropical region of eastern Asia and to characterize the southward outflow of continental pollution that prevails in the lower atmosphere during early spring. In this paper, we present the results for ozone, CO, NO, NOy ,S O2, 222 Radon, methane and C2–C8 nonmethane hydrocarbons (NMHCs), C1–C2 halocarbons, and C1–C5 alkyl nitrate measurements obtained between 19 February and 30 April 2001. The average mixing ratios of O3, CO, SO2, and NOy were 45 ppbv, 404 ppbv, 1.8 ppbv, and 10.4 ppbv, respectively. The two dominant NMHCs were ethane (mean: 2368 pptv) and ethyne (mean: 1402 pptv), followed by propane (814 pptv), toluene (540 pptv), benzene (492 pptv), ethene (498 pptv), and n-butane (326 pptv). The most abundant halocarbon was CH3Cl (mean: 821 pptv), while 2-BuONO2 and i-PrONO2 were the two dominant alkyl nitrates species with a mean mixing ratio of 20 pptv and 19 pptv, respectively. The levels of trace gases were strongly influenced by the outflow of continental air masses initiated by the passage of cold fronts. The data are segregated into four air mass groups according to the levels of 222 Rn and wind direction, representing fresh continental outflow, coastal, perturbed maritime, and local urban air. Ozone and CO showed a moderate positive correlation (r 2 = 0.4) in the marine air group, characterized by low 222 Rn and CO levels, but they were poorly correlated in the other air mass groups. SO2 and NOy exhibited good correlations (r 2 > 0.6) with each other but were poorly correlated with CO, indicating differences in their emission sources and/or removal processes. CO very strongly correlated with ethyne and benzene (r 2 > 0.85) and also showed good correlations with several other NMHCs. Moreover, CO correlated moderately with a biomass burning tracer (CH3Cl) and an urban/industrial tracer (C2Cl4) indicating the impact of mixed pollution from urban and biomass burning sources. The relationship of CO, SO2, and NOy with the indicator of atmospheric processing, ethyne/ CO and propane/ethane, were also examined. The 2001 data were compared to the results obtained in the same period in 1994 during PEM-West B. The mean ozone level in the spring of 2001 was much higher than during PEM-West B. SO2 also had higher concentrations during TRACE-P, while CO and NOy were comparable during the two campaigns. The observed difference has been discussed in the context of emission changes and variations in meteorology. Although it is difficult to draw definitive conclusions about the extent of the influence of these two factors, it appears that clearer skies and drier conditions may have been responsible for the higher ozone concentrations during the TRACE-P period. INDEX TERMS: 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry;

The Vertical Distribution of Radon in Clear and Cloudy Daytime Terrestrial Boundary Layers

Abstract Radon (222Rn) is a powerful natural tracer of mixing and exchange processes in the atmospheric boundary layer. The authors present and discuss the main features of a unique dataset of 50 high-resolution vertical radon profiles up to 3500 m above ground level, obtained in clear and cloudy daytime terrestrial boundary layers over an inland rural site in Australia using an instrumented motorized research glider. It is demonstrated that boundary layer radon profiles frequently exhibit a complex layered structure as a result of mixing and exchange processes of varying strengths and extents working in clear and cloudy conditions within the context of the diurnal cycle and the synoptic meteorology. Normalized aircraft radon measurements are presented, revealing the characteristic structure and variability of three major classes of daytime boundary layer: 1) dry convective boundary layers, 2) mixed layers topped with residual layers, and 3) convective boundary layers topped with coupled nonprecipitating ...

Separating remote fetch and local mixing influences on vertical radon measurements in the lower atmosphere

Two-point radon gradients provide a direct, unambiguous measure of near-surface atmospheric mixing. A 31-month data set of hourly radon measurements at 2 and 50 m is used to characterize the seasonality and diurnal variability of radon concentrations and gradients at a site near Sydney. Vertical differencing allows separation of remote (fetchrelated) effects on measured radon concentrations from those due to diurnal variations in the strength and extent of vertical mixing. Diurnal composites, grouped according to the maximum nocturnal radon gradient (Cmax), reveal strong connections between radon, wind, temperature and mixing depth on subdiurnal timescales. Comparison of the bulk Richardson Number (RiB) and the turbulence kinetic energy (TKE) with the radon-derived bulk diffusivity (KB) helps to elucidate the relationship between thermal stability, turbulence intensity and the resultant mixing. On nights with large Cmax, KB and TKE levels are low and RiB is well above the ‘critical’ value. Conversely, when Cmax is small, KB and TKE levels are high and RiB is near zero. For intermediate Cmax, however, RiB remains small whereas TKE and KB both indicate significantly reduced mixing. The relationship between stability and turbulence is therefore non-linear, with even mildly stable conditions being sufficient to suppress mixing.

Estimation of the molecular hydrogen soil uptake and traffic emissions at a suburban site near Paris through hydrogen, carbon monoxide, and radon-222 semicontinuous measurements

[1]xa0Since June 2006, simultaneous semicontinuous measurements of tropospheric molecular hydrogen (H2), carbon monoxide (CO), and radon-222 (222Rn) have been performed at Gif-sur-Yvette (Paris region), a suburban atmospheric measurement site in France. Molecular hydrogen mixing ratios range from 500 to 1000 ppb, CO mixing ratios vary from 100 to 1400 ppb, and 222Rn concentrations fluctuate from 0 to 20 Bq m−3. The H2 seasonal cycle shows the expected pattern for the Northern Hemisphere with a maximum in spring and a minimum in autumn. We inferred a mean baseline value of 533 ppb with a peak-to-peak amplitude of 30 ppb. Carbon monoxide exhibits a seasonal cycle with a maximum in winter and a minimum in summer. The mean baseline value reaches 132 ppb with a peak-to-peak amplitude of 40 ppb. Radon-222 presents weak seasonal variations with a maximum in autumn/winter and a minimum in spring/summer. The diurnal cycles of H2 and CO are dominated by emissions from nearby traffic with two peaks during morning and evening rush hours. The typical H2/CO emission ratio from traffic is found to be 0.47 ± 0.08 on a molar basis (ppb/ppb). The radon tracer method is applied to nighttime H2 observations to estimate the H2 soil uptake of the nocturnal catchment area of our sampling site. The influences from nocturnal local anthropogenic combustion sources are estimated by parallel measurements of CO at 0.14 × 10−5 g(H2) m−2 h−1. The mean inferred dry deposition velocity is 0.024 ± 0.013 cm s−1 with a seasonal amplitude of 40% at Gif-sur-Yvette.

Identifying tropospheric baseline air masses at Mauna Loa Observatory between 2004 and 2010 using Radon‐222 and back trajectories

[1]xa0We use 7u2009years of hourly radon observations at Mauna Loa Observatory (MLO), together with 10-day back trajectories, to identify baseline air masses at the station. The amplitude of the annual MLO radon cycle, based on monthly means, was 98 mBq m–3 (39 –137 mBq m–3), with maximum values in February (90th percentile 330 mBq m–3) and minimum values in August (10th percentile 8.1 mBq m–3). The composite diurnal radon cycle (amplitude 49 mBq m–3) is discussed with reference to the influences of local flow features affecting the site, and a 3-hour diurnal sampling window (0730–1030 HST) is proposed for observing the least terrestrially influenced tropospheric air masses. A set of 763 baseline events is selected, using the proposed sampling window together with trajectory information, and presented along with measured radon concentrations as a supplement. This data set represents a resource for the selection of baseline events at MLO for use with a range of trace species. A reduced set of 196 “deep baseline” events occurring in the July–September window is also presented and discussed. The distribution (10th/50th/90th percentile) of radon in deep-baseline events (8.7/29.2/66.1 mBq m–3) was considerably lower than that for the overall set of 763 baseline events (12.3/40.8/104.1 mBq m–3). Results from a simple budget calculation, using sonde-derived mixing depths and literature-based estimates of oceanic radon flux and radon concentrations in the marine boundary layer, indicate that the main source of residual radon in the lower troposphere under baseline conditions at MLO is downward mixing from aged terrestrial air masses in the upper troposphere.

Constraining annual and seasonal radon-222 flux density from the Southern Ocean using radon-222 concentrations in the boundary layer at Cape Grim

ABSTRACT Radon concentrations measured between 2001 and 2008 in marine air at Cape Grim, a baseline site in north-western Tasmania, are used to constrain the radon flux density from the Southern Ocean. A method is described for selecting hourly radon concentrations that are least perturbed by land emissions and dilution by the free troposphere. The distribution of subsequent radon flux density estimates is representative of a large area of the Southern Ocean, an important fetch region for Southern Hemisphere climate and air pollution studies. The annual mean flux density (0.27 mBq m−2 s−1) compares well with the mean of the limited number of spot measurements previously conducted in the Southern Ocean (0.24 mBq m−2 s−1), and to some spot measurements made in other oceanic regions. However, a number of spot measurements in other oceanic regions, as well as most oceanic radon flux density values assumed for modelling studies and intercomparisons, are considerably lower than the mean reported here. The reported radon flux varies with seasons and, in summer, with latitude. It also shows a quadratic dependence on wind speed and significant wave height, as postulated and measured by others, which seems to support our assumption that the selected least perturbed radon concentrations were in equilibrium with the oceanic radon source. By comparing the least perturbed radon observations in 2002–2003 with corresponding ‘TransCom’ model intercomparison results, the best agreement is found when assuming a normally distributed radon flux density with σ=0.075 mBq m−2 s−1.

Estimating the Asian radon flux density and its latitudinal gradient in winter using ground-based radon observations at Sado Island

Terrestrial radon-222 flux density for the Asian continent, integrated over distances of 4500 km, is estimated in two 20. latitudinal bands centred on 48.8.N and 63.2.N. The evaluation is based on three years of wintertime radon measurements at Sado Island, Japan, together with meteorological and trajectory information. A selection of 18% of observations are suitable for evaluation of an analytical expression for the continental surface flux. Various meteorological assumptions are discussed; it is found that there is a substantial effect of increased complexity of the formulation on the flux estimates obtained. The distribution of spatially integrated radon flux over the Asian landmass is reported for the first time. Expressed as geometric means and 1±-ranges, estimated fluxes are 14.1 mBq m.2 s.1 (1±-range: 18 mBq m-2 s-1) and 8.4 mBq m-2 s-1 (1±-range: 10 mBq m-2 s-1) for the lower and higher latitude bands. These results constitute an annual minimum in flux densities for these regions, and are higher than previously reported. The existence of a latitudinal gradient in the continental radon source function is confirmed; the present estimate for Asia (-0.39 mBq m-2 s-1 per degree of latitude) is in agreement with the northern hemisphere terrestrial radon flux gradient proposed previously.

Estimating the near-surface daily fine aerosol load using hourly Radon-222 observations

We investigate the extent to which hourly radon observations can be used to estimate daily PM2.5 loading near the ground. We formulate, test and apply a model that expresses the mean daily PM2.5 load as a linear combination of observed radon concentrations and differences on a given day. The model was developed using two consecutive years of observations (2007–2008) at four sites near Sydney, Australia, instrumented with aerosol samplers and radon detectors. Model performance was subsequently evaluated against observations in 2009. After successfully reproducing mean daily radon concentrations (r2≥0.98), we used the model to estimate daily PM2.5 mass, as well as that of selected elements (Si, K, Fe, Zn, H, S and Black Carbon). When parameterizing the model for elemental mass estimates the highest r2 values were generally obtained for H, BC, K and Si. Separating results by season, the r2 values for K and BC were higher in winter for all sites, a period of time where higher concentrations of these elements are seen and a rapid estimation tool would be of particular benefit. The best overall results were obtained in winter for H and BC [r2 = 0.50, 0.68, 0.70, 0.63 (H) and 0.57, 0.57, 0.78, 0.44 (BC)], respectively for Warrawong, Lucas Heights, Richmond and Muswellbrook. Evaluation of model PM2.5 estimates was most successful for days with typical aerosol loads; loads were usually underestimated for, the less frequent, high–to–extreme pollution days. The best elemental results were obtained for BC at Richmond in winter (r2 = 0.68). However, for Warrawong and Lucas Heights r2 values increased from 0.26 to 0.60, and from 0.33 to 0.73, respectively, when several particularly high concentration events were excluded from the analysis. The model performed best at Richmond, an inland site with relatively flat terrain. However, model parameters need to be evaluated for each site.

Synoptic variations in atmospheric CO2 at Cape Grim: a model intercomparison

A ‘TransCom’ model intercomparison is used to assess how well synoptic and diurnal variations of carbon dioxide (CO2) and 222Rn (radon) can be modelled at the coastal site, Cape Grim, Australia. Each model was run with prescribed fluxes and forced with analysed meteorology for 2000–2003. Twelve models were chosen for analysis based on each model’s ability to differentiate baseline CO2 concentrations from non-baseline CO2 (influenced by regional land fluxes). Analysis focused on non-baseline events during 2002–2003. Radon was better simulated than CO2, indicating that a spatially uniform radon land flux is a reasonable assumption and that regional-scale transport was adequately captured by the models. For both radon and CO2, the ensemble model mean generally performed better than any individual model. Two case studies highlight common problems with the simulations. First, in summer and autumn the Cape Grim observations are sometimes influenced by Tasmanian rather than mainland Australian fluxes. These periods are poorly simulated. Secondly, an event with an urban plume demonstrates how the relatively low spatial resolution of the input CO2 fluxes limits the quality of the simulations. Analysis of periods with below baseline concentration indicates the possible influence of carbon uptake by winter crops in southern mainland Australia.