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Long-lived metallic ions in the Earth's atmosphere (ionosphere) have been investigated for many decades. Although the seasonal variation in ionospheric “sporadic E” layers was first observed in the 1960s, the mechanism driving the variation remains a long-standing mystery. Here, we report a study of ionospheric irregularities using scintillation data from COSMIC satellites and identify a large-scale horizontal transport of long-lived metallic ions, combining the simulations of the Whole Atmosphere Community Climate Model with the chemistry of metals and ground-based observations from two meridional chains of stations from 1975–2016. We find that the lower thermospheric meridional circulation influences the meridional transport and seasonal variations of metallic ions within sporadic E layers. The winter-to-summer meridional velocity of ions is estimated to vary between −1.08 and 7.45 m/s at altitudes of 107–118 km between 10–60∘ N. Our results not only provide strong support for the lower thermospheric meridional circulation predicted by a whole atmosphere chemistry–climate model, but also emphasize the influences of this winter-to-summer circulation on the large-scale interhemispheric transport of composition in the thermosphere–ionosphere.

Mean temperatures in the polar summer mesopause can drop to 130 K. The low temperatures in combination with water vapor mixing ratios of a few parts per million give rise to the formation of ice particles. These ice particles may be observed as polar mesospheric clouds. Mesospheric ice cloud formation is believed to initiate heterogeneously on small aerosol particles (r 2O3 and FexSi1 − xO3) to realistic mesopause temperatures and water vapor concentrations and investigate particle warming under the influence of variable intensities of visible light (405, 488, and 660 nm). We show that Mie theory calculations using refractive indices of bulk material from the literature combined with an equilibrium temperature model presented in this work predict the particle warming very well. Additionally, we confirm that the absorption efficiency increases with the iron content of the MSP material. We apply our findings to mesopause conditions and conclude that the impact of solar and terrestrial radiation on ice particle formation is significantly lower than previously assumed.

© Author(s) 2018. This work is distributed under the Creative Commons Attribution 4.0 License (https://creativecommons.org/licenses/by/4.0/), Meteoric ablation produces layers of metal atoms in the mesosphere and lower thermosphere (MLT). It has been known for more than 30 years that the Ca atom layer is depleted by over 2 orders of magnitude compared with Na, despite these elements having nearly the same elemental abundance in chondritic meteorites. In contrast, the Ca+ ion abundance is depleted by less than a factor of 10. To explain these observations, a large database of neutral and ion-molecule reaction kinetics of Ca species, measured over the past decade, was incorporated into the Whole Atmosphere Community Climate Model (WACCM). A new meteoric input function for Ca and Na, derived using a chemical ablation model that has been tested experimentally with a Meteoric Ablation Simulator, shows that Ca ablates almost 1 order of magnitude less efficiently than Na. WACCM-Ca simulates the seasonal Ca layer satisfactorily when compared with lidar observations, but tends to overestimate Ca+ measurements made by rocket mass spectrometry and lidar. A key finding is that CaOH and CaCO3 are very stable reservoir species because they are involved in essentially closed reaction cycles with O2 and O. This has been demonstrated experimentally for CaOH, and in this study for CaCO3 using electronic structure and statistical rate theory. Most of the neutral Ca is therefore locked in these reservoirs, enabling rapid loss through polymerization into meteoric smoke particles, and this explains the extreme depletion of Ca.© Author(s) 2018., This work was supported by the European Research Council (project 291332 - CODITA). Shikha Raizada acknowledges NSF grant 1839012 to the Arecibo Observatory, which is operated by the University of Central Florida under a cooperative agreement with the National Science Foundation (AST-1744119), and in alliance with Yang Enterprises and Ana G. Mendez Universidad Metropolitana.

The University of Science and Technology of China narrowband sodium temperature and wind lidar, located in Hefei, China (32° N, 117° E), has made routine nighttime measurements since January 2012. A total of 154 nights (∼ 1400 h) of vertical profiles of temperature, sodium density, and zonal wind and 83 nights (∼ 800 h) of vertical flux of gravity wave (GW) zonal momentum in the mesopause region (80–105 km) were obtained during the period from 2012 to 2016. For temperature, it is most likely that the diurnal tide dominates below 100 km in spring, while the semidiurnal tide dominates above 100 km throughout the year. A clear semiannual variation in temperature is revealed near 90 km, in phase with the tropical mesospheric semiannual oscillation (MSAO). The variability in sodium density is positively correlated with temperature below 95 km, suggesting that in addition to dynamics, the chemistry also plays an important role in the formation of sodium atoms. The seasonal variability in sodium density observed by both lidar and satellite generally agrees well with a whole atmosphere model simulation using an updated meteoric input function which includes different cosmic dust sources. For zonal wind, the diurnal tide dominates in both spring and fall, while semidiurnal tide dominates in winter. The observed semiannual variation in zonal wind near 90 km is out of phase with that in temperature, consistent with the tropical MSAO. The lidar observations generally agree with satellite and meteor radar observations as well as model simulations at similar latitude. The 50–70 % of zonal momentum flux is induced by short-period (10 min–2 h) GWs. The large zonal momentum flux in summer and winter due to short-period GWs is clearly anticorrelated with eastward zonal wind maxima below 90 km, suggesting the filtering of short-period GWs by the SAO wind.

Accurate determination of the optical properties of analogues for meteoric smoke particles (MSPs), which are thought to be composed of iron-rich oxides or silicates, is important for their observation and characterization in the atmosphere. In this study, a photochemical aerosol flow system (PAFS) has been used to measure the optical extinction of iron oxide MSP analogues in the wavelength range 325–675 nm. The particles were made photochemically and agglomerate into fractal-like particles with sizes on the order of 100 nm. Analysis using transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS) suggested the particles were most likely maghemite-like (γ-Fe2O3) in composition, though a magnetite-like composition could not be completely ruled out. Assuming a maghemite-like composition, the optical extinction coefficients measured using the PAFS were combined with maghemite absorption coefficients measured using a complementary experimental system (the MICE-TRAPS) to derive complex refractive indices that reproduce both the measured absorption and extinction.

Lidar observations of the mesospheric Na layer have revealed considerable diurnal variations, particularly on the bottom side of the layer, where more than an order-of-magnitude increase in Na density has been observed below 80 km after sunrise. In this paper, multi-year Na lidar observations are utilized over a full diurnal cycle at Utah State University (USU) (41.8∘ N, 111.8∘ W) and a global atmospheric model of Na with 0.5 km vertical resolution in the mesosphere and lower thermosphere (WACCM-Na) to explore the dramatic changes of Na density on the bottom side of the layer. Photolysis of the principal reservoir NaHCO3 is shown to be primarily responsible for the increase in Na after sunrise, amplified by the increased rate of reaction of NaHCO3 with atomic H, which is mainly produced from the photolysis of H2O and the reaction of OH with O3. This finding is further supported by Na lidar observation at USU during the solar eclipse (>96 % totality) event on 21 August 2017, when a decrease and recovery of the Na density on the bottom side of the layer were observed. Lastly, the model simulation shows that the Fe density below around 80 km increases more strongly and earlier than observed Na changes during sunrise because of the considerably faster photolysis rate of its major reservoir of FeOH.

Fluorinated compounds such as NF3 and C2F5Cl (CFC-115) are characterised by very large global warming potentials (GWPs), which result from extremely long atmospheric lifetimes and strong infrared absorptions in the atmospheric window. In this study we have experimentally determined the infrared absorption cross sections of NF3 and CFC-115, calculated the radiative forcing and efficiency using two radiative transfer models and identified the effect of clouds and stratospheric adjustment. The infrared cross sections are within 10 % of previous measurements for CFC-115 but are found to be somewhat larger than previous estimates for NF3, leading to a radiative efficiency for NF3 that is 25 % larger than that quoted in the Intergovernmental Panel on Climate Change Fifth Assessment Report. A whole atmosphere chemistry–climate model was used to determine the atmospheric lifetimes of NF3 and CFC-115 to be (509 ± 21) years and (492 ± 22) years, respectively. The GWPs for NF3 are estimated to be 15 600, 19 700 and 19 700 over 20, 100 and 500 years, respectively. Similarly, the GWPs for CFC-115 are 6030, 7570 and 7480 over 20, 100 and 500 years, respectively.

A modelling study of radical chemistry in the coastal Antarctic boundary layer, based upon observations performed in the course of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign at Halley Research Station in coastal Antarctica during the austral summer 2004/2005, is described: a detailed zero-dimensional photochemical box model was used, employing inorganic and organic reaction schemes drawn from the Master Chemical Mechanism, with additional halogen (iodine and bromine) reactions added. The model was constrained to observations of long-lived chemical species, measured photolysis frequencies and meteorological parameters, and the simulated levels of HOx, NOx and XO compared with those observed. The model was able to replicate the mean levels and diurnal variation in the halogen oxides IO and BrO, and to reproduce NOx levels and speciation very well. The NOx source term implemented compared well with that directly measured in the course of the CHABLIS experiments. The model systematically overestimated OH and HO2 levels, likely a consequence of the combined effects of (a) estimated physical parameters and (b) uncertainties within the halogen, particularly iodine, chemical scheme. The principal sources of HOx radicals were the photolysis and bromine-initiated oxidation of HCHO, together with O(1D) + H2O. The main sinks for HOx were peroxy radical self- and cross-reactions, with the sum of all halogen-mediated HOx loss processes accounting for 40% of the total sink. Reactions with the halogen monoxides dominated CH3O2-HO2-OH interconversion, with associated local chemical ozone destruction in place of the ozone production which is associated with radical cycling driven by the analogous NO reactions. The analysis highlights the need for observations of physical parameters such as aerosol surface area and boundary layer structure to constrain such calculations, and the dependence of simulated radical levels and ozone loss rates upon a number of uncertain kinetic and photochemical parameters for iodine species.

Fluorescence Assay by Gas Expansion (FAGE) has been used to detect ambient levels of OH and HO2 radicals at the Cape Verde Atmospheric Observatory, located in the tropical Atlantic marine boundary layer, during May and June 2007. Midday radical concentrations were high, with maximum concentrations of 9 ×106 molecule cm−3 and 6×108 molecule cm−3 observed for OH and HO2, respectively. A box model incorporating the detailed Master Chemical Mechanism, extended to include halogen chemistry, heterogeneous loss processes and constrained by all available measurements including halogen and nitrogen oxides, has been used to assess the chemical and physical parameters controlling the radical chemistry. The model was able to reproduce the daytime radical concentrations to within the 1 σ measurement uncertainty of 20% during the latter half of the measurement period but significantly under-predicted [HO2] by 39% during the first half of the project. Sensitivity analyses demonstrate that elevated [HCHO] (~2 ppbv) on specific days during the early part of the project, which were much greater than the mean [HCHO] (328 pptv) used to constrain the model, could account for a large portion of the discrepancy between modelled and measured [HO2] at this time. IO and BrO, although present only at a few pptv, constituted ~19% of the instantaneous sinks for HO2, whilst aerosol uptake and surface deposition to the ocean accounted for a further 23% of the HO2 loss at noon. Photolysis of HOI and HOBr accounted for ~13% of the instantaneous OH formation. Taking into account that halogen oxides increase the oxidation of NOx (NO → NO2), and in turn reduce the rate of formation of OH from the reaction of HO2 with NO, OH concentrations were estimated to be 9% higher overall due to the presence of halogens. The increase in modelled OH from halogen chemistry gives an estimated 9% shorter lifetime for methane in this region, and the inclusion of halogen chemistry is necessary to model the observed daily cycle of O3 destruction that is observed at the surface. Due to surface losses, we hypothesise that HO2 concentrations increase with height and therefore contribute a larger fraction of the O3 destruction than at the surface.

The North Atlantic Marine Boundary Layer Experiment (NAMBLEX), involving over 50 scientists from 12 institutions, took place at Mace Head, Ireland (53.32° N, 9.90° W), between 23 July and 4 September 2002. A wide range of state-of-the-art instrumentation enabled detailed measurements of the boundary layer structure and atmospheric composition in the gas and aerosol phase to be made, providing one of the most comprehensive in situ studies of the marine boundary layer to date. This overview paper describes the aims of the NAMBLEX project in the context of previous field campaigns in the Marine Boundary Layer (MBL), the overall layout of the site, a summary of the instrumentation deployed, the temporal coverage of the measurement data, and the numerical models used to interpret the field data. Measurements of some trace species were made for the first time during the campaign, which was characterised by predominantly clean air of marine origin, but more polluted air with higher levels of NOx originating from continental regions was also experienced. This paper provides a summary of the meteorological measurements and Planetary Boundary Layer (PBL) structure measurements, presents time series of some of the longer-lived trace species (O3, CO, H2, DMS, CH4, NMHC, NOx, NOy, PAN) and summarises measurements of other species that are described in more detail in other papers within this special issue, namely oxygenated VOCs, HCHO, peroxides, organo-halogenated species, a range of shorter lived halogen species (I2, OIO, IO, BrO), NO3 radicals, photolysis frequencies, the free radicals OH, HO2 and (HO2+Σ RO2), as well as a summary of the aerosol measurements. NAMBLEX was supported by measurements made in the vicinity of Mace Head using the NERC Dornier-228 aircraft. Using ECMWF wind-fields, calculations were made of the air-mass trajectories arriving at Mace Head during NAMBLEX, and were analysed together with both meteorological and trace-gas measurements. In this paper a chemical climatology for the duration of the campaign is presented to interpret the distribution of air-mass origins and emission sources, and to provide a convenient framework of air-mass classification that is used by other papers in this issue for the interpretation of observed variability in levels of trace gases and aerosols.

Several zero-dimensional box-models with different levels of chemical complexity, based on the Master Chemical Mechanism (MCM), have been used to study the chemistry of OH and HO2 in a coastal environment in the Northern Hemisphere. The models were constrained to and compared with measurements made during the NAMBLEX campaign (Mace Head, Ireland) in summer 2002. The base models, which were constrained to measured CO, CH4 and NMHCs, were able to reproduce [OH] within 25%, but overestimated [HO2] by about a factor of 2. Agreement was improved when the models were constrained to oxygenated compounds (acetaldehyde, methanol and acetone), highlighting their importance for the radical budget. When the models were constrained to measured halogen monoxides (IO, BrO) and used a more detailed, measurements-based, treatment to describe the heterogeneous uptake, modelled [OH] increased by up to 15% and [HO2] decreased by up to 30%. The actual impact of halogen monoxides on the modelled concentrations of HOx was dependant on the uptake coefficients used for HOI, HOBr and HO2. Better agreement, within the combined uncertainties of the measurements and of the model, was achieved when using high uptake coefficients for HO2 and HOI (γHO2=1, γHOI=0.6). A rate of production and destruction analysis of the models allowed a detailed study of OH and HO2 chemistry under the conditions encountered during NAMBLEX, showing the importance of oxygenates and of XO (where X=I, Br) as co-reactants for OH and HO2 and of HOX photolysis as a source for OH.

Peroxy radical (HO2+ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in the European continental boundary layer.

The formation, evolution and eventual sublimation of noctilucent clouds (NLC) may have a significant effect on the odd oxygen and hydrogen chemistry of the high latitude summer mesosphere. Three mechanisms are considered here: the direct uptake of atomic oxygen on the surface of the ice particles; the redistribution of water vapour, which changes the photochemical source of odd hydrogen species; and the direct photolysis of the ice particles themselves to produce odd hydrogen species in the gas phase. A 1-D photochemical model is employed to investigate the potential importance of these mechanisms. This shows, using the recently measured uptake coefficients of O on ice, that the heterogeneous removal of O on the surface of the cloud particles is too slow by at least a factor of 5x103 to compete with gas-phase O chemistry. The second and third mechanisms involve the solar Lyman-α photolysis of H2O in the gas and solid phase, respectively. During twilight, Lyman-α radiation is severely attenuated and these mechanisms are insignificant. In contrast, when the upper mesosphere is fully illuminated there is a dramatic impact on the O profile, with depletion of O at the base of the cloud layer of close to an order of magnitude. A correspondingly large depletion in O3 is also predicted, while H, OH, HO2 and H2O2 are found to be enhanced by factors of 3-5. In fact, rocket-borne mass spectrometer measurements during summer have revealed local H2O2 enhancements in the region of the clouds. Rocket-borne measurements of atomic O and O3 profiles in the presence of mesospheric clouds in the daytime are highly desirable to test the predictions of this model and our understanding of the genesis of mesospheric clouds.

Mg and Mg+ concentration fields in the upper mesosphere/lower thermosphere (UMLT) region are retrieved from SCIAMACHY/Envisat limb measurements of Mg and Mg+ dayglow emissions using a 2-D tomographic retrieval approach. The time series of monthly mean Mg and Mg+ number density and vertical column density in different latitudinal regions are presented. Data from the limb mesosphere–thermosphere mode of SCIAMACHY/Envisat are used, which cover the 50 to 150 km altitude region with a vertical sampling of ≈3.3 km and latitudes up to 82°. The high latitudes are not observed in the winter months, because there is no dayglow emission during polar night. The measurements were performed every 14 days from mid-2008 until April 2012. Mg profiles show a peak at around 90 km altitude with a density between 750 cm−3 and 1500 cm−3. Mg does not show strong seasonal variation at latitudes below 40°. For higher latitudes the density is lower and only in the Northern Hemisphere a seasonal cycle with a summer minimum is observed. The Mg+ peak occurs 5–15 km above the neutral Mg peak altitude. These ions have a significant seasonal cycle with a summer maximum in both hemispheres at mid and high latitudes. The strongest seasonal variations of Mg+ are observed at latitudes between 20 and 40° and the density at the peak altitude ranges from 500 cm−3 to 4000 cm−3. The peak altitude of the ions shows a latitudinal dependence with a maximum at mid latitudes that is up to 10 km higher than the peak altitude at the equator. The SCIAMACHY measurements are compared to other measurements and WACCM model results. The WACCM results show a significant seasonal variability for Mg with a summer minimum, which is more clearly pronounced than for SCIAMACHY, and globally a higher peak density than the SCIAMACHY results. Although the peak density of both is not in agreement, the vertical column density agrees well, because SCIAMACHY and WACCM profiles have different widths. The agreement between SCIAMACHY and WACCM results is much better for Mg+ with both showing the same seasonality and similar peak density. However, there are also minor differences, e.g. WACCM showing a nearly constant altitude of the Mg+ layer's peak density for all latitudes and seasons.

The atmospheric chemistry of iodine and bromine in Polar regions is of interest due to the key role of halogens in many atmospheric processes, particularly tropospheric ozone destruction. Bromine is emitted from the open ocean but is enriched above first-year sea ice during springtime bromine explosion events, whereas iodine emission is attributed to biological communities in the open ocean and hosted by sea ice. It has been previously demonstrated that bromine and iodine are present in Antarctic ice over glacial–interglacial cycles. Here we investigate seasonal variability of bromine and iodine in polar snow and ice, to evaluate their emission, transport and deposition in Antarctica and the Arctic and better understand potential links to sea ice. We find that bromine and iodine concentrations and Br enrichment (relative to sea salt content) in polar ice do vary seasonally in Arctic snow and Antarctic ice. Although seasonal variability in halogen emission sources is recorded by satellite-based observations of tropospheric halogen concentrations, seasonal patterns observed in snowpack are likely also influenced by photolysis-driven processes. Peaks of bromine concentration and Br enrichment in Arctic snow and Antarctic ice occur in spring and summer, when sunlight is present. A secondary bromine peak, observed at the end of summer, is attributed to bromine deposition at the end of the polar day. Iodine concentrations are largest in winter Antarctic ice strata, contrary to contemporary observations of summer maxima in iodine emissions. These findings support previous observations of iodine peaks in winter snow strata attributed to the absence of sunlight-driven photolytic re-mobilisation of iodine from surface snow. Further investigation is required to confirm these proposed mechanisms explaining observations of halogens in polar snow and ice, and to evaluate the extent to which halogens may be applied as sea ice proxies.

International audience; Time series observations of molecular iodine (I2), iodine oxides (IO, OIO), bromine oxide (BrO), and the nitrate radical (NO3) in the mid-latitude coastal marine boundary layer (MBL) are reported. Measurements were made using a new long-path DOAS instrument during a summertime campaign at Mace Head on the B3Π(0+u)-X1?+g electronic transition between 535 and 575 nm. The I2 mixing ratio was found to vary from below the detection limit (~5 ppt) up to a nighttime maximum of 93 ppt. Along with I2, observations of IO, OIO and NO3 were also made during the night. Surprisingly, IO and OIO were detected at mixing ratios up to 2.5 and 10.8 ppt, respectively. A model is employed to show that the reaction between I2 and NO3 is the likely nighttime source of these radicals. The BrO mixing ratio varied from below the detection limit at night (~1 ppt) to a maximum of 6 ppt in the first hours after sunrise. A bromine chemistry model is used to simulate the diurnal behaviour of the BrO radical, demonstrating the importance of halogen recycling through sea-salt aerosol. In the same campaign a zenith sky DOAS was employed to determine the column density variation of NO3 as a function of solar zenith angle (SZA) during sunrise, from which vertical profiles of NO3 through the troposphere were obtained. On several occasions a positive gradient of NO3 was observed over the first 2 km, possibly due to dimethyl sulphide (DMS) removing NO3 at the ocean surface.

International audience; A time-resolved model of the Na layer in the mesosphere/lower thermosphere region is described, where the continuity equations for the major sodium species Na, Na+ and NaHCO3 are solved explicity, and the other short-lived species are treated in steady-state. It is shown that the diurnal variation of the Na layer can only be modelled satisfactorily if sodium species are permanently removed below about 85 km, both through the dimerization of NaHCO3 and the uptake of sodium species on meteoric smoke particles that are assumed to have formed from the recondensation of vaporized meteoroids. When the sensitivity of the Na layer to the meteoroid input function is considered, an inconsistent picture emerges. The ratio of the column abundance of Na+ to Na is shown to increase strongly with the average meteoroid velocity, because the Na is injected at higher altitudes. Comparison with a limited set of Na+ measurements indicates that the average meteoroid velocity is probably less than about 25 km s-1, in agreement with velocity estimates from conventional meteor radars, and considerably slower than recent observations made by wide aperture incoherent scatter radars. The Na column abundance is shown to be very sensitive to the meteoroid mass input rate, and to the rate of vertical transport by eddy diffusion. Although the magnitude of the eddy diffusion coefficient in the 80?90 km region is uncertain, there is a consensus between recent models using parameterisations of gravity wave momentum deposition that the average value is less than 3×105 cm2 s-1. This requires that the global meteoric mass input rate is less than about 20 td-1, which is closest to estimates from incoherent scatter radar observations. Finally, the diurnal variation in the meteoroid input rate only slight perturbs the Na layer, because the residence time of Na in the layer is several days, and diurnal effects are effectively averaged out.

No abstract available.

NOx measurements were conducted at the Halley Research Station, coastal Antarctica, during the austral summer period 1 January–10 February 2005. A clear NOx diurnal cycle was observed with minimum concentrations close to instrumental detection limit (5 pptv) measured between 04:00–05:00 GMT. NOx concentrations peaked (24 pptv) between 19:00–20:00 GMT, approximately 5 h after local solar noon. An optimised box model of NOx concentrations based on production from in-snow nitrate photolysis and chemical loss derives a mean noon emission rate of 3.48 × 108 molec cm−2 s−1, assuming a 100 m boundary layer mixing height, and a relatively short NOx lifetime of ~6.4 h. This emission rate compares to directly measured values ranging from 2.1 to 12.6 × 108 molec cm−2 s−1 made on 3 days at the end of the study period. Calculations of the maximum rate of NO2 loss via a variety of conventional HOx and halogen oxidation processes show that the lifetime of NOx is predominantly controlled by halogen processing, namely BrNO3 and INO3 gas-phase formation and their subsequent heterogeneous uptake. Furthermore the presence of halogen oxides is shown to significantly perturb NOx concentrations by decreasing the NO/NO2 ratio. We conclude that in coastal Antarctica, the potential ozone production efficiency of NOx emitted from the snowpack is mitigated by the more rapid NOx loss due to halogen nitrate hydrolysis.