Abstract.Radon is increasingly being used as a tool for quantifying stability influences on urban pollutant concentrations. Bulk radon gradients are ideal for this purpose, since the vertical differencing substantially removes contributions from processes on timescales greater than diurnal and (assuming a constant radon source) gradients are directly related to the intensity of nocturnal mixing. More commonly, however, radon measurements are available only at a single height. In this study we argue that single-height radon observations should not be used quantitatively as an indicator of atmospheric stability without prior conditioning of the time series to remove contributions from larger-scale "nonlocal" processes. We outline a simple technique to obtain an approximation of the diurnal radon gradient signal from a single-height measurement time series, and use it to derive a four category classification scheme for atmospheric stability on a "whole night" basis. A selection of climatological and pollution observations in the Sydney region are then subdivided according to the radon-based scheme on an annual and seasonal basis. We compare the radon-based scheme against a commonly used Pasquill-Gifford (P-G) type stability classification and reveal that the most stable category in the P-G scheme is less selective of the strongly stable nights than the radon-based scheme; this lead to significant underestimation of pollutant concentrations on the most stable nights by the P-G scheme. Lastly, we applied the radon-based classification scheme to mixing height estimates calculated from the diurnal radon accumulation time series, which provided insight to the range of nocturnal mixing depths expected at the site for each of the stability classes.

Representation of atmospheric transport is a major source of error in the estimation of greenhouse gas sources and sinks by inverse modelling. Here we assess the impact on trace gas mole fractions of the new physical parameterizations recently implemented in the atmospheric global climate model LMDz to improve vertical diffusion, mesoscale mixing by thermal plumes in the planetary boundary layer (PBL), and deep convection in the troposphere. At the same time, the horizontal and vertical resolution of the model used in the inverse system has been increased. The aim of this paper is to evaluate the impact of these developments on the representation of trace gas transport and chemistry, and to anticipate the implications for inversions of greenhouse gas emissions using such an updated model. Comparison of a one-dimensional version of LMDz with large eddy simulations shows that the thermal scheme simulates shallow convective tracer transport in the PBL over land very efficiently, and much better than previous versions of the model. This result is confirmed in three-dimensional simulations, by a much improved reproduction of the radon-222 diurnal cycle. However, the enhanced dynamics of tracer concentrations induces a stronger sensitivity of the new LMDz configuration to external meteorological forcings. At larger scales, the inter-hemispheric exchange is slightly slower when using the new version of the model, bringing them closer to observations. The increase in the vertical resolution (from 19 to 39 layers) significantly improves the representation of stratosphere/troposphere exchange. Furthermore, changes in atmospheric thermodynamic variables, such as temperature, due to changes in the PBL mixing modify chemical reaction rates, which perturb chemical equilibriums of reactive trace gases. One implication of LMDz model developments for future inversions of greenhouse gas emissions is the ability of the updated system to assimilate a larger amount of high-frequency data sampled at high-variability stations. Others implications are discussed at the end of the paper

We demonstrate the ability of atmospheric radon concentrations to reliably and unambiguously identify local and remote terrestrial influences on an air mass, and thereby the potential for alteration of trace gas composition by anthropogenic and biogenic processes. Based on high accuracy (lower limit of detection 10-40 mBq m -3 ), high temporal resolution (hourly) measurements of atmospheric radon concentration we describe, apply and evaluate a simple two-step method for identifying and characterising constituent mole fractions in baseline air. The technique involves selecting a radon-based threshold concentration to identify the "cleanest" (least terrestrially influenced) air masses, and then performing an outlier removal step based on the distribution of constituent mole fractions in the identified clean air masses. The efficacy of this baseline selection technique is tested at three contrasting WMO GAW stations: Cape Grim (a coastal low-altitude site), Mauna Loa (a remote high-altitude island site), and Jungfraujoch (a continental high-altitude site). At Cape Grim and Mauna Loa the two-step method is at least as effective as more complicated methods employed to characterise baseline conditions, some involving up to nine steps. While it is demonstrated that Jungfraujoch air masses rarely meet the baseline criteria of the more remote sites, a selection method based on a variable monthly radon threshold is shown to produce credible "near baseline" characteristics. The seasonal peak-to-peak amplitude of recent monthly baseline CO 2 mole fraction deviations from the long-term trend at Cape Grim, Mauna Loa and Jungfraujoch are estimated to be 1.1, 6.0 and 8.1 ppm, respectively.

Abstract. Mercury is a toxic element of serious concern for human and environmental health. Understanding its natural cycling in the environment is an important goal towards assessing its impacts and the effectiveness of mitigation strategies. Due to the unique chemical and physical properties of mercury, the atmosphere is the dominant transport pathway for this heavy metal, with the consequence that regions far removed from sources can be impacted. However, there exists a dearth of long-term monitoring of atmospheric mercury, particularly in the tropics and Southern Hemisphere. This paper presents the first 2 years of gaseous elemental mercury (GEM) measurements taken at the Australian Tropical Atmospheric Research Station (ATARS) in northern Australia, as part of the Global Mercury Observation System (GMOS). Annual mean GEM concentrations determined at ATARS (0.95 ± 0.12 ng m −3 ) are consistent with recent observations at other sites in the Southern Hemisphere. Comparison with GEM data from other Australian monitoring sites suggests a concentration gradient that decreases with increasing latitude. Seasonal analysis shows that GEM concentrations at ATARS are significantly lower in the distinct wet monsoon season than in the dry season. This result provides insight into alterations of natural mercury cycling processes as a result of changes in atmospheric humidity, oceanic/terrestrial fetch, and convective mixing, and invites future investigation using wet mercury deposition measurements. Due to its location relative to the atmospheric equator, ATARS intermittently samples air originating from the Northern Hemisphere, allowing an opportunity to gain greater understanding of inter-hemispheric transport of mercury and other atmospheric species. Diurnal cycles of GEM at ATARS show distinct nocturnal depletion events that are attributed to dry deposition under stable boundary layer conditions. These cycles provide strong further evidence supportive of a "multihop" model of GEM cycling, characterised by multiple surface depositions and re-emissions, in addition to long-range transport through the atmosphere.

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