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The influence of nonmigrating diurnal tides on Na layer variability in the mesosphere and lower thermosphere regions is investigated for the first time using data from the Optical Spectrograph and InfraRed Imaging System (OSIRIS) on the Odin satellite and Specified Dynamics Whole Atmosphere Community Climate Model (SD-WACCM) with metal chemistry. The Na density from OSIRIS exhibits a clear longitudinal variation indicative of the presence of tidal components. Similar variability is seen in the SD-WACCM result. Analysis shows a significant relationship between the nonmigrating diurnal tides in Na density and the corresponding temperature tidal signal. Below 90 km, the three nonmigrating diurnal tidal components in Na density show a significant positive correlation with the temperature tides. Conversely, the phase mainly indicates a negative correlation above 95 km. Around the metal layer peak, the response of the Na density to a 1 K change in tidal temperature is estimated to be 120 cm−3.

The Earth's mesopause region between about 75 and 105 km is characterised by chemiluminescent emission from various lines of different molecules and atoms. This emission was and is important for the study of the chemistry and dynamics in this altitude region at nighttime. However, our understanding is still very limited with respect to molecular emissions with low intensities and high line densities that are challenging to resolve. Based on 10 years of data from the astronomical X-shooter echelle spectrograph at Cerro Paranal in Chile, we have characterised in detail this nightglow (pseudo-)continuum in the wavelength range from 300 to 1800 nm. We studied the spectral features, derived continuum components with similar variability, calculated climatologies, studied the response to solar activity, and even estimated the effective emission heights. The results indicate that the nightglow continuum at Cerro Paranal essentially consists of only two components, which exhibit very different properties. The main structures of these components peak at 595 and 1510 nm. While the former was previously identified as the main peak of the FeO “orange arc” bands, the latter is a new discovery. Laboratory data and theory indicate that this feature and other structures between about 800 and at least 1800 nm are caused by emission from the low-lying A′′ and A′ states of HO2. In order to test this assumption, we performed runs with the Whole Atmosphere Community Climate Model (WACCM) with modified chemistry and found that the total intensity, layer profile, and variability indeed support this interpretation, where the excited HO2 radicals are mostly produced from the termolecular recombination of H and O2. The WACCM results for the continuum component that dominates at visual wavelengths show good agreement for FeO from the reaction of Fe and O3. However, the simulated total emission appears to be too low, which would require additional mechanisms where the variability is dominated by O3. A possible (but nevertheless insufficient) process could be the production of excited OFeOH by the reaction of FeOH and O3.

This article begins with a review of important advances in the chemistry and related physics of the mesosphere and lower thermosphere (MLT) region of the atmosphere that have occurred over the past 2 decades, since the founding of Atmospheric Chemistry and Physics. The emphasis here is on chemistry, but we also discuss recent findings on atmospheric dynamics and forcings to the extent that these are important for understanding MLT composition and chemistry. Topics that are covered include observations, with satellite, rocket and ground-based techniques; the variability and connectedness of the MLT on various length scales and timescales; airglow emissions; the cosmic dust input and meteoric metal layers; and noctilucent/polar mesospheric ice clouds. The paper then concludes with a discussion of important unanswered questions and likely future directions for the field over the next decade.

Satellite- and aircraft-based mid-infrared measurements of polar stratospheric clouds (PSCs) have provided spectroscopic evidence for the presence of β-NAT (nitric acid trihydrate) particles. Metastable nitric acid hydrate phases such as α-NAT and α-NAD (nitric acid dihydrate) have been frequently observed in laboratory experiments but not yet detected as a constituent of PSCs in atmospheric measurements. As for the β-NAD modification, its formation was first observed in X-ray diffraction measurements when the low-temperature α-NAD phase was warmed to a temperature above 210 K. Its infrared spectrum has been reported, but so far no optical constants have been derived that could be used as input for infrared retrievals of PSC composition. In this work, we show that β-NAD particles were efficiently formed in isothermal heterogeneous crystallisation experiments at 190 K from supercooled HNO3/H2O solution droplets containing an embedded mineral dust or meteoric smoke particle analogue. An inversion algorithm based on a T-matrix optical model was used to derive for the first time the mid-infrared complex refractive indices of the β-NAD modification from the measured extinction spectrum of the particles. In contrast to the heterogeneous crystallisation experiments, the α-NAD phase was formed when the HNO3/H2O solution droplets did not contain a solid nucleus and crystallised homogeneously. Using a light-scattering detector that recorded two-dimensional scattering patterns of the crystallised NAD particles, we were able to determine predominant shapes of the α- and β-NAD crystals. We found that α-NAD grew into elongated, needle-shaped crystals, while β-NAD particles were compact in shape. This agrees with previously reported images of α- and β-NAD particles grown on the cryo-stage of an environmental scanning electron microscope. While direct evidence for the existence of metastable NAD in the polar stratosphere is still lacking, our experiments add to the wealth of previous laboratory studies that have identified various conditions for the rapid growth of metastable compositions. In the atmosphere, these could be intermediate states that transform into thermodynamically stable NAT on longer timescales in aged PSCs.

The crystal formation of nitric acid trihydrate (NAT) in the absence of water ice is important for a subset of polar stratospheric clouds (PSCs) and thereby ozone depletion. It has been suggested that either fragmented meteoroids or meteoric smoke particles (MSPs), or possibly both, are important as heterogeneous nuclei of these crystals. Previous work has focused on the nucleating ability of meteoric material in nitric acid in the absence of sulfuric acid. However, it is known that when immersed in stratospheric sulfuric acid droplets, metal-containing meteoric material particles partially dissolve and components can reprecipitate as silica and alumina that have different morphologies to the original meteoric material. Hence, in this study, we experimentally and theoretically explore the relative role that sulfuric acid-processed MSPs and meteoric fragments may play in NAT nucleation in PSCs. We compared meteoric fragments that had recently been prepared (by milling a meteorite sample) to a sample annealed under conditions designed to simulate heating during entry into the Earth's atmosphere. Whilst the addition of sulfuric acid decreased the nucleating ability of the recently milled meteoric material relative to nucleation in binary nitric acid-water solutions (at similar NAT saturation ratio), the annealed meteoric fragments nucleated NAT with a similar effectiveness in both solutions. However, combining our results with measured fluxes of meteoric material to the Earth, sedimentation modelling and recent experiments on fragmentation of incoming meteoroids suggests that it is unlikely for there to be sufficient fragments to contribute to the nucleation of crystalline NAT particles. We then considered silica formed from sulfuric acid-processed MSPs. Our previous work showed that nanoparticulate silica (radius ∼6 nm) is a relatively poor promoter of nucleation compared with micron-scaled silica particles, which were more effective. Both materials have similar chemical and structural (crystallographically amorphous) properties, indicating that size is critical. Here, we account for surface curvature of primary grains using the Classical Nucleation Theory (CNT) to explore this size dependence. This model is able to explain the discrepancy in nucleation effectiveness of fumed silica and fused quartz by treating their nucleating activity (contact angle) as equal but with differing particle size (or surface curvature), assuming interfacial energies that are physically reasonable. Here, we use this CNT model to present evidence that nucleation of NAT on acid-processed MSPs, where the primary grain size is tens of nanometres, is also effective enough to contribute to NAT crystals in early season PSCs where there is an absence of ice. This study demonstrates that the modelling of crystal nucleation in PSCs and resulting ozone depletion relies on an accurate understanding of the transport and chemical processing of MSPs. This will affect estimated sensitivity of stratospheric chemistry to rare events such as large volcanic eruptions and long-term forecasting of ozone recovery in a changing climate.

The ground-based measurements obtained from a lidar network and the 6-year OSIRIS (optical spectrograph and infrared imager system) limb-scanning radiance measurements made by the Odin satellite are used to study the climatology of the middle- and low-latitude sodium (Na) layer. Up to January 2021, four Na resonance fluorescence lidars at Beijing (40.5∘ N, 116.0∘ E), Hefei (31.8∘ N, 117.3∘ E), Wuhan (30.5∘ N, 114.4∘ E), and Haikou (19.5∘ N, 109.1∘ E) collected vertical profiles of Na density for a total of 2136 nights (19 587 h). These large datasets provide multi-year routine measurements of the Na layer with exceptionally high temporal and vertical resolution. The lidar measurements are particularly useful for filling in OSIRIS data gaps since the OSIRIS measurements were not made during the dark winter months because they utilize the solar-pumped resonance fluorescence from Na atoms. The observations of Na layers from the ground-based lidars and the satellite are comprehensively compared with a global model of meteoric Na in the atmosphere (WACCM–Na). The lidars present a unique test of OSIRIS and WACCM (Whole Atmosphere Community Climate Model), because they cover the latitude range along 120∘ E longitude in an unusual geographic location with significant gravity wave generation. In general, good agreement is found between lidar observations, satellite measurements, and WACCM simulations. On the other hand, the Na number density from OSIRIS is larger than that from the Na lidars at the four stations within one standard deviation of the OSIRIS monthly average, particularly in autumn and early winter arising from significant uncertainties in Na density retrieved from much less satellite radiance measurements. WACCM underestimates the seasonal variability of the Na layer observed at the lower latitude lidar stations (Wuhan and Haikou). This discrepancy suggests the seasonal variability of vertical constituent transport modelled in WACCM is underestimated because much of the gravity wave spectrum is not captured in the model.

The NCAR Whole Atmosphere Community Climate Model with thermosphere and ionosphere eXtension (WACCM-X) v2.1 has been extended to include the neutral and ion–molecule chemistry and dynamics of three metals (Mg, Na, and Fe), which are injected into the upper mesosphere–lower thermosphere by meteoric ablation. Here we focus on the self-consistent electrodynamical transport of metallic ions in both the E and F regions. The model with full ion transport significantly improves the simulation of global distribution and seasonal variations of Mg+, although the peak density is slightly lower (about 35 % lower in peak density) compared with the SCIAMACHY measurements. Near the magnetic equator, the diurnal variation in upward and downward transport of Mg+ is generally consistent with the “ionosphere fountain effect”. The thermospheric distribution of Fe is shown to be closely coupled to the transport of Fe+. The effect of ion mass on ion transport is also examined: the lighter ions (Mg+ and Na+) are transported above 150 km more easily than the heavy Fe+. We also examine the impact of the transport of major molecular ions, NO+ and O2+, on the distribution of metallic ions.

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.

Iodine oxides (IxOy) play an important role in the atmospheric chemistry of iodine. They are initiators of new particle formation events in the coastal and polar boundary layers and act as iodine reservoirs in tropospheric ozone-depleting chemical cycles. Despite the importance of the aforementioned processes, the photochemistry of these molecules has not been studied in detail previously. Here, we report the first determination of the absorption cross sections of IxOy, x=2, 3, 5, y=1–12 at λ=355 nm by combining pulsed laser photolysis of I2∕O3 gas mixtures in air with time-resolved photo-ionization time-of-flight mass spectrometry, using NO2 actinometry for signal calibration. The oxides selected for absorption cross-section determinations are those presenting the strongest signals in the mass spectra, where signals containing four iodine atoms are absent. The method is validated by measuring the absorption cross section of IO at 355 nm, σ355nm,IO= (1.2±0.1) ×10-18 cm2, which is found to be in good agreement with the most recent literature. The results obtained are σ355nm,I2O3<5×10-19 cm2 molec.−1, σ355nm,I2O4= (3.9±1.2)×10-18 cm2 molec.−1, σ355nm,I3O6= (6.1±1.6)×10-18 cm2 molec.−1, σ355nm,I3O7= (5.3±1.4)×10-18 cm2 molec.−1, and σ355nm,I5O12= (9.8±1.0)×10-18 cm2 molec.−1. Photodepletion at λ=532 nm was only observed for OIO, which enabled determination of upper limits for the absorption cross sections of IxOy at 532 nm using OIO as an actinometer. These measurements are supplemented with ab initio calculations of electronic spectra in order to estimate atmospheric photolysis rates J(IxOy). Our results confirm a high J(IxOy) scenario where IxOy is efficiently removed during daytime, implying enhanced iodine-driven ozone depletion and hindering iodine particle formation. Possible I2O3 and I2O4 photolysis products are discussed, including IO3, which may be a precursor to iodic acid (HIO3) in the presence of HO2.

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.

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.

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.

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.

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.

Heterogeneous nucleation of crystalline nitric acid hydrates in polar stratospheric clouds (PSCs) enhances ozone depletion. However, the identity and mode of action of the particles responsible for nucleation remains unknown. It has been suggested that meteoric material may trigger nucleation of nitric acid trihydrate (NAT, or other nitric acid phases), but this has never been quantitatively demonstrated in the laboratory. Meteoric material is present in two forms in the stratosphere: smoke that results from the ablation and re-condensation of vapours, and fragments that result from the break-up of meteoroids entering the atmosphere. Here we show that analogues of both materials have a capacity to nucleate nitric acid hydrates. In combination with estimates from a global model of the amount of meteoric smoke and fragments in the polar stratosphere we show that meteoric material probably accounts for NAT observations in early season polar stratospheric clouds in the absence of water ice.

During the last decade, several limb sounding satellites have measured the global sodium (Na) number densities in the mesosphere and lower thermosphere (MLT). Datasets are now available from Global Ozone Monitoring by Occultation of Stars (GOMOS), the SCanning Imaging Absorption spectroMeter for Atmospheric CHartography (SCIAMACHY) (both on Envisat) and the Optical Spectrograph and InfraRed Imager System (OSIRIS) (on Odin). Furthermore, global model simulations of the Na layer in the MLT simulated by the Whole Atmosphere Community Climate Model, including the Na species (WACCM-Na), are available. In this paper, we compare these global datasets.The observed and simulated monthly averages of Na vertical column densities agree reasonably well with each other. They show a clear seasonal cycle with a summer minimum most pronounced at the poles. They also show signs of a semi-annual oscillation in the equatorial region. The vertical column densities vary from 0. 5 × 109 to 7 × 109 cm−2 near the poles and from 3 × 109 to 4 × 109 cm−2 at the Equator. The phase of the seasonal cycle and semi-annual oscillation shows small differences between the Na amounts retrieved from different instruments. The full width at half maximum of the profiles is 10 to 16 km for most latitudes, but significantly smaller in the polar summer. The centroid altitudes of the measured sodium profiles range from 89 to 95 km, whereas the model shows on average 2 to 4 km lower centroid altitudes. This may be explained by the mesopause being 3 km lower in the WACCM simulations than in measurements. Despite this global 2–4 km shift, the model captures well the latitudinal and temporal variations. The variation of the WACCM dataset during the year at different latitudes is similar to the one of the measurements. Furthermore, the differences between the measured profiles with different instruments and therefore different local times (LTs) are also present in the model-simulated profiles. This capturing of latitudinal and temporal variations is also found for the vertical column densities and profile widths.

Airglow emission lines of OH, O2, O and Na are commonly used to probe the MLT (mesosphere–lower thermosphere) region of the atmosphere. Furthermore, molecules like electronically excited NO, NiO and FeO emit a (pseudo-) continuum. These continua are harder to investigate than atomic emission lines. So far, limb-sounding from space and a small number of ground-based low-to-medium resolution spectra have been used to measure FeO emission in the MLT. In this study the medium-to-high resolution echelle spectrograph X-shooter at the Very Large Telescope (VLT) in the Chilean Atacama Desert (24°37′ S, 70°24′ W; 2635 m) is used to study the FeO pseudo-continuum in the range from 0.5 to 0.72 µm based on 3662 spectra. Variations of the FeO spectrum itself, as well as the diurnal and seasonal behaviour of the FeO and Na emission intensities, are reported. These airglow emissions are linked by their common origin, meteoric ablation, and they share O3 as a common reactant. Major differences are found in the main emission peak of the FeO airglow spectrum between 0.58 and 0.61 µm, compared with a theoretical spectrum. The FeO and Na airglow intensities exhibit a similar nocturnal variation and a semi-annual seasonal variation with equinoctial maxima. This is satisfactorily reproduced by a whole atmosphere chemistry climate model, if the quantum yields for the reactions of Fe and Na with O3 are 13 ± 3 and 11 ± 2 % respectively. However, a comparison between the modelled O3 in the upper mesosphere and measurements of O3 made with the SABER satellite instrument suggests that these quantum yields may be a factor of ∼ 2 smaller.

We have used the Whole Atmosphere Community Climate Model (WACCM), with an updated treatment of loss processes, to determine the atmospheric lifetime of sulfur hexafluoride (SF6). The model includes the following SF6 removal processes: photolysis, electron attachment and reaction with mesospheric metal atoms. The Sodankylä Ion Chemistry (SIC) model is incorporated into the standard version of WACCM to produce a new version with a detailed D region ion chemistry with cluster ions and negative ions. This is used to determine a latitude- and altitude-dependent scaling factor for the electron density in the standard WACCM in order to carry out multi-year SF6 simulations. The model gives a mean SF6 lifetime over an 11-year solar cycle (τ) of 1278 years (with a range from 1120 to 1475 years), which is much shorter than the currently widely used value of 3200 years, due to the larger contribution (97.4 %) of the modelled electron density to the total atmospheric loss. The loss of SF6 by reaction with mesospheric metal atoms (Na and K) is far too slow to affect the lifetime. We investigate how this shorter atmospheric lifetime impacts the use of SF6 to derive stratospheric age of air. The age of air derived from this shorter lifetime SF6 tracer is longer by 9 % in polar latitudes at 20 km compared to a passive SF6 tracer. We also present laboratory measurements of the infrared spectrum of SF6 and find good agreement with previous studies. We calculate the resulting radiative forcings and efficiencies to be, on average, very similar to those reported previously. Our values for the 20-, 100- and 500-year global warming potentials are 18 000, 23 800 and 31 300, respectively.

Studies of transitionally dense meteor trails using radars which employ specularly reflecting interferometric techniques are used to show that measurable high-temperature chemistry exists at timescales of a few tenths of a second after the formation of these trails. This is a process which is distinct from the ambient-temperature chemistry that is already known to exist at timescales of tens of seconds and longer in long-lived trails. As a consequence, these transitionally dense trails have smaller lifetimes than might be expected if diffusion were the only mechanism for reducing the mean trail electron density. The process has been studied with four SKiYMET radars at latitudes varying from 10 to 75° N, over a period of more than 10 years, 24 h per day. In this paper we present the best parameters to use to represent this behaviour and demonstrate the characteristics of the temporal and latitudinal variability in these parameters. The seasonal, day–night and latitudinal variations correlate reasonably closely with the corresponding variations of ozone in the upper mesosphere. Possible reasons for these effects are discussed, but further investigations of any causative relation are still the subject of ongoing studies.

Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I2 during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I2 could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO3+ HOI → IO + HNO3 is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260–300 K and at a pressure of 1000 hPa to be k(T) = 2.7 × 10−12 (300 K/T)2.66 cm3 molecule−1 s−1. This reaction is included in two atmospheric models, along with the known reaction between I2 and NO3, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I2, which results in the enhancement of more than 25 % of nighttime ocean emissions of HOI + I2 and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO3 radical levels in the marine boundary layer (MBL) and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation.

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.

This study presents a new ion–neutral chemical model coupled into the Whole Atmosphere Community Climate Model (WACCM). The ionospheric D-region (altitudes ∼ 50–90 km) chemistry is based on the Sodankylä Ion Chemistry (SIC) model, a one-dimensional model containing 307 ion–neutral and ion recombination, 16 photodissociation and 7 photoionization reactions of neutral species, positive and negative ions, and electrons. The SIC mechanism was reduced using the simulation error minimization connectivity method (SEM-CM) to produce a reaction scheme of 181 ion–molecule reactions of 181 ion–molecule reactions of 27 positive and 18 negative ions. This scheme describes the concentration profiles at altitudes between 20 km and 120 km of a set of major neutral species (HNO3, O3, H2O2, NO, NO2, HO2, OH, N2O5) and ions (O2+, O4+, NO+, NO+(H2O), O2+(H2O), H+(H2O), H+(H2O)2, H+(H2O)3, H+(H2O)4, O3−, NO2−, O−, O2, OH−, O2−(H2O), O2−(H2O)2, O4−, CO3−, CO3−(H2O), CO4−, HCO3−, NO2−, NO3−, NO3−(H2O), NO3−(H2O)2, NO3−(HNO3), NO3−(HNO3)2, Cl−, ClO−), which agree with the full SIC mechanism within a 5 % tolerance. Four 3-D model simulations were then performed, using the impact of the January 2005 solar proton event (SPE) on D-region HOx and NOx chemistry as a test case of four different model versions: the standard WACCM (no negative ions and a very limited set of positive ions); WACCM-SIC (standard WACCM with the full SIC chemistry of positive and negative ions); WACCM-D (standard WACCM with a heuristic reduction of the SIC chemistry, recently used to examine HNO3 formation following an SPE); and WACCM-rSIC (standard WACCM with a reduction of SIC chemistry using the SEM-CM method). The standard WACCM misses the HNO3 enhancement during the SPE, while the full and reduced model versions predict significant NOx, HOx and HNO3 enhancements in the mesosphere during solar proton events. The SEM-CM reduction also identifies the important ion–molecule reactions that affect the partitioning of odd nitrogen (NOx), odd hydrogen (HOx) and O3 in the stratosphere and mesosphere.

Ice-nucleating particles can modify cloud properties with implications for climate and the hydrological cycle; hence, it is important to understand which aerosol particle types nucleate ice and how efficiently they do so. It has been shown that aerosol particles such as natural dusts, volcanic ash, bacteria and pollen can act as ice-nucleating particles, but the ice-nucleating ability of combustion ashes has not been studied. Combustion ashes are major by-products released during the combustion of solid fuels and a significant amount of these ashes are emitted into the atmosphere either during combustion or via aerosolization of bottom ashes. Here, we show that combustion ashes (coal fly ash, wood bottom ash, domestic bottom ash, and coal bottom ash) nucleate ice in the immersion mode at conditions relevant to mixed-phase clouds. Hence, combustion ashes could play an important role in primary ice formation in mixed-phase clouds, especially in clouds that are formed near the emission source of these aerosol particles. In order to quantitatively assess the impact of combustion ashes on mixed-phase clouds, we propose that the atmospheric abundance of combustion ashes should be quantified since up to now they have mostly been classified together with mineral dust particles. Also, in reporting ice residue compositions, a distinction should be made between natural mineral dusts and combustion ashes in order to quantify the contribution of combustion ashes to atmospheric ice nucleation.

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.

Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4) and methane sulfonic acid (MSA) were measured in NE Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected-ion chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 104 cm−3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analyzed in conjunction with the condensational sink for both compounds derived from 3 nm to 10 μm (aerodynamic diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed, leading to estimated atmospheric lifetimes on the order of 7 and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal, evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s), its ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated H2SO4 concentrations were consistently lower than the measured concentrations by a factor of 4.7 ± 2.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D), and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photolysis and photooxidation of biogenic iodine compounds. As to the identity of the atmospheric SO2 oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on {ab initio} calculations. Never\-theless, IO could contribute significantly to the observed CIMS background signal. A detailed analysis of this CIMS background signal in context with recently published kinetic data currently suggests that Criegee intermediates (CIs) produced from ozonolysis of alkenes play no significant role for SO2 oxidation in the marine atmosphere at Mace Head. On the other hand, SO2 oxidation by small CIs such as CH2OO produced photolytically or possibly in the photochemical degradation of methane is consistent with our observations. In addition, H2SO4 formation from dimethyl sulfide oxidation via SO3 as an intermediate instead of SO2 also appears to be a viable explanation. Both pathways need to be further explored.

We report and analyse the characteristics of 1382 meteor trails based on a sodium data set of ~ 680 h. The observations were made at Yanqing (115.97° E, 40.47° N), China by a ground-based Na fluorescence lidar. The temporal resolution of the raw profiles is 1.5 s and the altitude resolution is 96 m. We discover some characteristics of meteor trails different from those presented in previous reports. The occurrence heights of the trails follow a double-peak distribution with the peaks at ~ 83.5 km and at ~ 95.5 km, away from the peak height of the regular Na layer. 4.7% of the trails occur below 80 km, and 3.25% above 100 km. 75% of the trails are observed in only one 1.5 s profile, suggesting that the dwell time in the laser beam is not greater than 1.5 s. The peak density of the trails as a function of height is similar to that of the background sodium layer. The raw occurrence height distribution is corrected taking account of three factors which affect the relative lifetime of a trail as a function of height: the meteoroid velocity (which controls the ratio of Na/Na+ ablated); diffusional spreading of the trail; and chemical removal of Na. As a result, the bi-modal distribution is more pronounced. Modelling results show that the higher peak corresponds to a meteoroid population with speeds between 20 and 30 km s−1, whereas the lower peak should arise from much slower particles in a near-prograde orbit. It is inferred that most meteoroids in this data set have masses of ~ 1 mg, in order for ablation to produce sufficient Na atoms to be detected by lidar. Finally, the evolution of longer-duration meteor trails is investigated. Signals at each altitude channel consist of density enhancement bursts with the growth process usually faster than the decay process, and there exists a progressive phase shift among these altitude channels.

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.

Reactive iodine compounds play a significant role in the atmospheric chemistry of the oceanic boundary layer by influencing the oxidising capacity through catalytically removing O3 and altering the HOx and NOx balance. The sea-to-air flux of iodine over the open ocean is therefore an important quantity in assessing these impacts on a global scale. This paper examines the effect of a number of relevant environmental parameters, including water temperature, salinity and organic compounds, on the magnitude of the HOI and I2 fluxes produced from the uptake of O3 and its reaction with iodide ions in aqueous solution. The results of these laboratory experiments and those reported previously (Carpenter et al., 2013), along with sea surface iodide concentrations measured or inferred from measurements of dissolved total iodine and iodate reported in the literature, were then used to produce parameterised expressions for the HOI and I2 fluxes as a function of wind speed, sea-surface temperature and O3. These expressions were used in the Tropospheric HAlogen chemistry MOdel (THAMO) to compare with MAX-DOAS measurements of iodine monoxide (IO) performed during the HaloCAST-P cruise in the eastern Pacific ocean (Mahajan et al., 2012). The modelled IO agrees reasonably with the field observations, although significant discrepancies are found during a period of low wind speeds (< 3 m s−1), when the model overpredicts IO by up to a factor of 3. The inorganic iodine flux contributions to IO are found to be comparable to, or even greater than, the contribution of organo-iodine compounds and therefore its inclusion in atmospheric models is important to improve predictions of the influence of halogen chemistry in the marine boundary layer.

Sea ice is an important parameter in the climate system and its changes impact upon the polar albedo and atmospheric and oceanic circulation. Iodine (I) and bromine (Br) have been measured in a shallow firn core drilled at the summit of the Holtedahlfonna glacier (Northwest Spitsbergen, Svalbard). Changing I concentrations can be linked to the March–May maximum sea ice extension. Bromine enrichment, indexed to the Br / Na sea water mass ratio, appears to be influenced by changes in the seasonal sea ice area. I is emitted from marine biota and so the retreat of March–May sea ice coincides with enlargement of the open-ocean surface which enhances marine primary production and consequent I emission. The observed Br enrichment could be explained by greater Br emissions during the Br explosions that have been observed to occur mainly above first year sea ice during the early springtime. In this work we present the first comparison between halogens in surface snow and Arctic sea ice extension. Although further investigation is required to characterize potential depositional and post-depositional processes, these preliminary findings suggest that I and Br can be linked to variability in the spring maximum sea ice extension and seasonal sea ice surface area.

Sea ice is an integral part of the earth's climate system because it affects planetary albedo, sea-surface salinity, and the atmosphere–ocean exchange of reactive gases and aerosols. Bromine and iodine chemistry is active at polar sea ice margins with the occurrence of bromine explosions and the biological production of organoiodine from sea ice algae. Satellite measurements demonstrate that concentrations of bromine oxide (BrO) and iodine oxide (IO) decrease over sea ice toward the Antarctic interior. Here we present speciation measurements of bromine and iodine in the TALDICE (TALos Dome Ice CorE) ice core (159°11' E, 72°49' S; 2315 m a.s.l.) spanning the last 215 ky. The Talos Dome ice core is located 250 km inland and is sensitive to marine air masses intruding onto the Antarctic Plateau. Talos Dome bromide (Br−) is positively correlated with temperature and negatively correlated with sodium (Na). Based on the Br−/Na seawater ratio, bromide is depleted in the ice during glacial periods and enriched during interglacial periods. Total iodine, consisting of iodide (I−) and iodate (IO3−), peaks during glacials with lower values during interglacial periods. Although IO3− is considered the most stable iodine species in the atmosphere it was only observed in the TALDICE record during glacial maxima. Sea ice dynamics are arguably the primary driver of halogen fluxes over glacial–interglacial timescales, by altering the distance between the sea ice edge and the Antarctic plateau and by altering the surface area of sea ice available to algal colonization. Based on our results we propose the use of both halogens for examining Antarctic variability of past sea ice extent.

Ship-based Multi-Axis Differential Optical Absorption Spectroscopy measurements of iodine monoxide (IO) and atmospheric and seawater Gas Chromatography-Mass Spectrometer observations of methyl iodide (CH3I) were made in the Eastern Pacific marine boundary layer during April 2010 as a part of the HaloCarbon Air Sea Transect-Pacific (HaloCAST-P) scientific cruise. The presence of IO in the open ocean environment was confirmed, with a maximum differential slant column density of 5 × 1013 molecules cm−2 along the 1° elevation angle (corresponding to approximately 1 pptv) measured in the oligotrophic region of the Southeastern Pacific. Such low IO mixing ratios and their observed geographical distribution are inconsistent with satellite estimates and with previous understanding of oceanic sources of iodine. A strong correlation was observed between reactive iodine (defined as IO + I) and CH3I, suggesting common sources. In situ measurements of meteorological parameters and physical ocean variables, along with satellite-based observations of Chlorophyll a (Chl a) and Chromophoric Dissolved Organic Matter (CDOM) were used to gain insight into the possible sources of iodine in this remote environment. Surprisingly, reactive iodine showed a negative correlation (> 99% confidence) to Chl a and CDOM across the cruise transect. However, a significant positive correlation (> 99% confidence) with sea surface temperature (SST) and salinity instead suggests a widespread abiotic source related to the availability of aqueous iodine and to temperature.

We present in situ observations of meteoric smoke particles (MSP) obtained during three sounding rocket flights in December 2010 in the frame of the final campaign of the Norwegian-German ECOMA project (ECOMA = Existence and Charge state Of meteoric smoke particles in the Middle Atmosphere). The flights were conducted before, at the maximum activity, and after the decline of the Geminids which is one of the major meteor showers over the year. Measurements with the ECOMA particle detector yield both profiles of naturally charged particles (Faraday cup measurement) as well as profiles of photoelectrons emitted by the MSPs due to their irradiation by photons of a xenon-flash lamp. The column density of negatively charged MSPs decreased steadily from flight to flight which is in agreement with a corresponding decrease of the sporadic meteor flux recorded during the same period. This implies that the sporadic meteors are a major source of MSPs while the additional influx due to the shower meteors apparently did not play any significant role. Surprisingly, the profiles of photoelectrons are only partly compatible with this observation: while the photoelectron current profiles obtained during the first and third flight of the campaign showed a qualitatively similar behaviour as the MSP charge density data, the profile from the second flight (i.e., at the peak of the Geminids) shows much smaller photoelectron currents. This may tentatively be interpreted as a different MSP composition (and, hence, different photoelectric properties) during this second flight, but at this stage we are not in a position to conclude that there is a cause and effect relation between the Geminids and this observation. Finally, the ECOMA particle detector used during the first and third flight employed three instead of only one xenon flash lamp where each of the three lamps used for one flight had a different window material resulting in different cut off wavelengths for these three lamp types. Taking into account these data along with simple model estimates as well as rigorous quantum chemical calculations, it is argued that constraints on MSP sizes, work function and composition can be inferred. Comparing the measured data to a simple model of the photoelectron currents, we tentatively conclude that we observed MSPs in the 0.5–3 nm size range with generally increasing particle size with decreasing altitude. Notably, this size information can be obtained because different MSP particle sizes are expected to result in different work functions which is both supported by simple classical arguments as well as quantum chemical calculations. Based on this, the MSP work function can be estimated to lie in the range from ~4–4.6 eV. Finally, electronic structure calculations indicate that the low work function of the MSP measured by ECOMA indicates that Fe and Mg hydroxide clusters, rather than metal silicates, are the major constituents of the smoke particles.

Iodine oxide particles are known to nucleate in the marine boundary layer where gas phase molecular iodine and organoiodine species are produced by macroalgae. These ultra-fine particles may then grow through the condensation of other materials to sizes where they may serve as cloud condensation nuclei. There has been some debate over the chemical identity of the initially nucleated particles. In laboratory simulations, hygroscopic measurements have been used to infer that they are composed of insoluble I2O4, while elemental analysis of laboratory generated particles suggests soluble I2O5 or its hydrated form iodic acid, HIO3 (I2O5·H2O). In this paper we explore the response of super-micron sized aqueous iodic acid solution droplets to varying humidity using both Raman microscopy and single particle electrodynamic traps. These measurements reveal that the propensity of an iodic acid solution droplet to crystallise is negligible on drying to ~0% relative humidity (RH). On applying mechanical pressure to these droplets they shatter in a manner consistent with an ultra-viscous liquid or a brittle glass. Water retention in amorphous material at low RH is important for understanding the hygroscopic growth of aerosol particles and uptake of other condensable material. Subsequent water uptake between 10 and 20% RH causes their viscosity to reduce sufficiently that the cracked droplets flow and merge. The persistence of iodic acid solution in an amorphous state, rather than a crystalline state, suggests they will more readily accommodate other condensable material and are therefore more likely to grow to sizes where they may serve as cloud condensation nuclei. On increasing the humidity to ~90% the mass of the droplets only increases by ~20% with a corresponding increase in radius of only 6%, which is remarkably small for a highly soluble material. We suggest that the small growth factor of aqueous iodic acid solution droplets is consistent with the small aerosol growth factors observed in previous experiments.

Tropical rainforests act as a huge contributor to the global emissions of biogenic volatile organic compounds (BVOCs). Measurements of their oxidation products, such as formaldehyde (HCHO) and glyoxal (CHOCHO), provide useful indicators of fast photochemistry occurring in the lower troposphere. However, measurements of these species in tropical forest locations are extremely limited. To redress this, HCHO and CHOCHO were measured using the long-path (LP) and multi-axis (MAX) differential optical absorption spectroscopy (DOAS) techniques above the rainforest canopy in Borneo during two campaigns in spring and summer 2008, as part of the Oxidant and Particle Photochemical Processes above a south-east Asian tropical rainforest (OP3) project. The results were compared with concurrent measurements of hydroxyl radical (OH), isoprene (C5H8) (which was the dominant organic species emitted in this forest environment), and various meteorological parameters. Formaldehyde was observed at a maximum concentration of 4.5 ppb and glyoxal at a maximum of 1.6 ppb, significantly higher than previous measurements in rural locations. A 1-D chemistry model was then used to assess the diurnal evolution of formaldehyde and glyoxal throughout the boundary layer. The results, which compare well with the LP-DOAS and MAX-DOAS observations, suggest that the majority of the glyoxal and formaldehyde is confined to the first 500 m of the boundary layer, and that the measured ratio of these species is reproduced using currently accepted product yields for the oxidation of isoprene by OH. An important conclusion is that the measured levels of glyoxal are consistent with the surprisingly high concentrations of OH measured in this environment.

We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately −0.10 W m−2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m−2 contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone.

Nano-sized meteoric smoke particles (MSPs) with iron-magnesium silicate compositions, formed in the upper mesosphere as a result of meteoric ablation, may remove sulphuric acid from the gas-phase above 40 km and may also affect the composition and behaviour of supercooled H2SO4-H2O droplets in the global stratospheric aerosol (Junge) layer. This study describes a time-resolved spectroscopic analysis of the evolution of the ferric (Fe3+) ion originating from amorphous ferrous (Fe2+)-based silicate powders dissolved in varying Wt % sulphuric acid (30–75 %) solutions over a temperature range of 223–295 K. Complete dissolution of the particles was observed under all conditions. The first-order rate coefficient for dissolution decreases at higher Wt % and lower temperature, which is consistent with the increased solution viscosity limiting diffusion of H2SO4 to the particle surfaces. Dissolution under stratospheric conditions should take less than a week, and is much faster than the dissolution of crystalline Fe2+ compounds. The chemistry climate model UMSLIMCAT (based on the UKMO Unified Model) was then used to study the transport of MSPs through the middle atmosphere. A series of model experiments were performed with different uptake coefficients. Setting the concentration of 1.5 nm radius MSPs at 80 km to 3000 cm−3 (based on rocket-borne charged particle measurements), the model matches the reported Wt % Fe values of 0.5–1.0 in Junge layer sulphate particles, and the MSP optical extinction between 40 and 75 km measured by a satellite-borne spectrometer, if the global meteoric input rate is about 20 tonnes per day. The model indicates that an uptake coefficient ≥0.01 is required to account for the observed two orders of magnitude depletion of H2SO4 vapour above 40 km.

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.

Simultaneous measurements of atomic iodine (I), molecular iodine (I2) and ultrafine particles were made at O Grove, Galicia (42.50° N, 8.87° W), on the northwest coast of Spain. The observations show a strong tidal signature, and indicate that the most probable sources of reactive iodine species are the exposed macroalgae during low tide. For the first time, I2 and I were concurrently measured revealing a high average I2/I ratio of ~32, which is higher than previously inferred by modelling studies. A 1-dimensional photochemical model is employed to simulate the observations showing that the high I2/I ratio can be reproduced in the presence of fast vertical mixing close to the surface, or using an extra chemical loss for I atoms with an unknown species. There is a lack of strong correlation between the I2/I and ultrafine particles, indicating that although they both have macroalgal sources, these were not at the same location. The model simulations also suggest that the source of the observed ultrafine particles is likely not very close to the measurement site, in order for the particles to form and grow, but the source for I and I2 must be local. Finally, the effect of NOx levels on iodine oxides, and the conditions under which iodine particle bursts will be suppressed, are explored.

Iodine emissions from the dominant six macroalgal species in the coastal regions around Roscoff, France, have been modelled to support the Reactive Halogens in the Marine Boundary Layer Experiment (RHaMBLe) undertaken in September 2006. A two-dimensional model is used to explore the relationship between geographically resolved regional emissions (based on maps of seaweed beds in the area and seaweed I2 emission rates previously measured in the laboratory) and in situ point and line measurements of I2 performed respectively by a broadband cavity ringdown spectroscopy (BBCRDS) instrument sited on the shoreline and a long-path differential optical absorption spectroscopy (LP-DOAS) instrument sampling over an extended light path to an off-shore island. The modelled point and line I2 concentrations compare quantitatively with BBCRDS and LP-DOAS measurements, and provide a link between emission fields and the different measurement geometries used to quantify atmospheric I2 concentrations during RHaMBLe. Total I2 emissions over the 100 km2 region around Roscoff are calculated to be 1.7×1019 molecules per second during the lowest tides. During the night, the model replicates I2 concentrations up to 50 pptv measured along the LP-DOAS instrument's line of sight, and predicts spikes of several hundred pptv in certain conditions. Point I2 concentrations up to 50 pptv are also calculated at the measurement site, in broad agreement with the BBCRDS observations. Daytime measured concentrations of I2 at the site correlate with modelled production and transport processes. However substantial recycling of the photodissociated I2 is required for the model to quantitatively match measured concentrations. This result corroborates previous modelling of iodine and NOx chemistry in the semi-polluted marine boundary layer which proposed a mechanism for recycling I2 via the formation, transport and subsequent reactions of the IONO2 reservoir compound. The methodology presented in this paper provides a tool for linking spatially distinct measurements to inhomogeneous and temporally varying emission fields.

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.

Although tropospheric reactive halogen chemistry is well studied in coastal and polar environments, the presence of halogens over the open ocean environment has not been widely reported. The impacts of halogens on the tropical open ocean marine boundary layer (MBL), in particular, are not well characterised. This paper describes observations of iodine monoxide (IO) and bromine oxide (BrO) over eight months in the tropical open ocean MBL, on the north-eastern side of São Vicente (Cape Verde Islands, 16.85° N, 24.87° W). The highest BrO mixing ratio observed was 5.6±1 pmol mol−1, while the maximum observed IO mixing ratio was 3.1±0.4 pmol mol−1. The average values seen between 09:00–17:00 GMT were ~2.8 pmol mol−1 for BrO and ~1.5 pmol mol−1 for IO; these averages showed little variability over the entire campaign from November 2006 to June 2007. A 1-dimensional chemistry and transport model is used to study the evolution of iodine species and quantify the combined impact of iodine and bromine chemistry on the oxidising capacity of the MBL. It appears that the measured fluxes of iodocarbons are insufficient to account for the observed levels of IO, and that an additional I atom source is required, possibly caused by the deposition of O3 onto the ocean surface in the presence of solar radiation. Modelling results also show that the O3 depletion observed at Cape Verde cannot be explained in the absence of halogen chemistry, which contributes ~45% of the observed O3 depletion at the height of measurements (10 m) during summer. The model also predicts that halogens decrease the hydroperoxy radical (HO2) concentration by ~14% and increase the hydroxyl radical (OH) concentration by ~13% near the ocean surface. The oxidation of dimethyl sulphide (DMS) by BrO takes place at a comparable rate to oxidation by OH in this environment. Finally, the potential of iodine chemistry to form new particles is explored and conditions under which particle formation could be important in the remote MBL are discussed.

Point source measurements of IO by laser induced fluorescence spectroscopy were made at a semi-polluted coastal location during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) campaign in September 2006. The site, on the NW French coast in Roscoff, was characterised by extensive intertidal macroalgae beds which were exposed at low tide. The closest known iodine active macroalgae beds were at least 300 m from the measurement point. From 20 days of measurements, IO was observed above the instrument limit of detection on 14 days, of which a clear diurnal profile was observed on 11 days. The maximum IO mixing ratio was 30.0 pptv (10 s integration period) during the day, amongst the highest concentrations ever observed in the atmosphere, and 1–2 pptv during the night. IO concentrations were strongly dependent on tidal height, the intensity of solar irradiation and meteorological conditions. An intercomparison of IO measurements made using point source and spatially averaged DOAS instruments confirms the presence of hot-spots of IO caused by an inhomogeneous distribution of macroalgae. The co-incident, point source measurement of IO and ultra fine particles (2.5 nm≥d≥10 nm) displayed a strong correlation, providing evidence that IO is involved in the production pathway of ultra fine particles at coastal locations. Finally, a modelling study shows that high IO concentrations which are likely to be produced in a macrolagae rich environment can significantly perturb the concentrations of OH and HO2 radicals. The effect of IO on HOx is reduced as NOx concentrations increase.

This paper presents a summary of the measurements made during the heavily-instrumented Reactive Halogens in the Marine Boundary Layer (RHaMBLe) coastal study in Roscoff on the North West coast of France throughout September 2006. It was clearly demonstrated that iodine-mediated coastal particle formation occurs, driven by daytime low tide emission of molecular iodine, I2, by macroalgal species fully or partially exposed by the receding waterline. Ultrafine particle concentrations strongly correlate with the rapidly recycled reactive iodine species, IO, produced at high concentrations following photolysis of I2. The heterogeneous macroalgal I2 sources lead to variable relative concentrations of iodine species observed by path-integrated and in situ measurement techniques. Apparent particle emission fluxes were associated with an enhanced apparent depositional flux of ozone, consistent with both a direct O3 deposition to macroalgae and involvement of O3 in iodine photochemistry and subsequent particle formation below the measurement height. The magnitude of the particle formation events was observed to be greatest at the lowest tides with the highest concentrations of ultrafine particles growing to the largest sizes, probably by the condensation of anthropogenically-formed condensable material. At such sizes the particles should be able to act as cloud condensation nuclei at reasonable atmospheric supersaturations.

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.

Nanoparticles of iron oxide (crystalline and amorphous), silicon oxide and magnesium oxide were investigated for their propensity to nucleate ice over the temperature range 180–250 K, using the AIDA chamber in Karlsruhe, Germany. All samples were observed to initiate ice formation via the deposition mode at threshold ice super-saturations (RHithresh) ranging from 105% to 140% for temperatures below 220 K. Approximately 10% of amorphous Fe2O3 particles (modal diameter = 30 nm) generated in situ from a photochemical aerosol reactor, led to ice nucleation at RHithresh = 140% at an initial chamber temperature of 182 K. Quantitative analysis using a singular hypothesis treatment provided a fitted function [ns(190 K)=10(3.33×sice)+8.16] for the variation in ice-active surface site density (ns:m−2) with ice saturation (sice) for Fe2O3 nanoparticles. This was implemented in an aerosol-cloud model to determine a predicted deposition (mass accommodation) coefficient for water vapour on ice of 0.1 at temperatures appropriate for the upper atmosphere. Classical nucleation theory was used to determine representative contact angles (θ) for the different particle compositions. For the in situ generated Fe2O3 particles, a slight inverse temperature dependence was observed with θ = 10.5° at 182 K, decreasing to 9.0° at 200 K (compared with 10.2° and 11.4° respectively for the SiO2 and MgO particle samples at the higher temperature). These observations indicate that such refractory nanoparticles are relatively efficient materials for the nucleation of ice under the conditions studied in the chamber which correspond to cirrus cloud formation in the upper troposphere. The results also show that Fe2O3 particles do not act as ice nuclei under conditions pertinent for tropospheric mixed phase clouds, which necessarily form above ~233 K. At the lower temperatures (

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol−1 and nmol mol−1 to reflect common practice). Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

In April–July 2008, intensive measurements were made of atmospheric composition and chemistry in Sabah, Malaysia, as part of the "Oxidant and particle photochemical processes above a South-East Asian tropical rainforest" (OP3) project. Fluxes and concentrations of trace gases and particles were made from and above the rainforest canopy at the Bukit Atur Global Atmosphere Watch station and at the nearby Sabahmas oil palm plantation, using both ground-based and airborne measurements. Here, the measurement and modelling strategies used, the characteristics of the sites and an overview of data obtained are described. Composition measurements show that the rainforest site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO2 and HCHO. The dominant modulators of atmospheric chemistry at the rainforest site were therefore emissions of BVOCs and soil emissions of reactive nitrogen oxides. At the observed BVOC:NOx volume mixing ratio (~100 pptv/pptv), current chemical models suggest that daytime maximum OH concentrations should be ca. 105 radicals cm−3, but observed OH concentrations were an order of magnitude greater than this. We confirm, therefore, previous measurements that suggest that an unexplained source of OH must exist above tropical rainforest and we continue to interrogate the data to find explanations for this.

Most of the extraterrestrial dust entering the Earth's atmosphere ablates to produce metal vapours, which have significant effects on the aeronomy of the upper mesosphere and lower thermosphere. A new Chemical Ablation Model (CAMOD) is described which treats the physics and chemistry of ablation, by including the following processes: sputtering by inelastic collisions with air molecules before the meteoroid melts; evaporation of atoms and oxides from the molten particle; diffusion-controlled migration of the volatile constituents (Na and K) through the molten particle; and impact ionization of the ablated fragments by hyperthermal collisions with air molecules. Evaporation is based on thermodynamic equilibrium in the molten meteoroid (treated as a melt of metal oxides), and between the particle and surrounding vapour phase. The loss rate of each element is then determined assuming Langmuir evaporation. CAMOD successfully predicts the meteor head echo appearance heights, observed from incoherent scatter radars, over a wide range of meteoroid velocities. The model also confirms that differential ablation explains common-volume lidar observations of K, Ca and Ca+ in fresh meteor trails. CAMOD is then used to calculate the injection rates into the atmosphere of a variety of elements as a function of altitude, integrated over the meteoroid mass and velocity distributions. The most abundant elements (Fe, Mg and Si) have peak injection rates around 85 km, with Na and K about 8 km higher. The more refractory element Ca ablates around 82 km with a Na:Ca ratio of 4:1, which does therefore not explain the depletion of atomic Ca to Na, by more than 2 orders of magnitude, in the upper mesosphere. Diffusion of the most volatile elements (Na and K) does not appear to be rate-limiting except in the fastest meteoroids. Non-thermal sputtering causes ~35% mass loss from the fastest (~60–70 km s−1) and smallest (10−17–10−13 g) meteoroids, but makes a minor contribution to the overall ablation rate.

CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) was a collaborative UK research project aimed at probing the detailed chemistry of the Antarctic boundary layer and the exchange of trace gases at the snow surface. The centre-piece to CHABLIS was the measurement campaign, conducted at the British Antarctic Survey station, Halley, in coastal Antarctica, from January 2004 through to February 2005. The campaign measurements covered an extremely wide range of species allowing investigations to be carried out within the broad context of boundary layer chemistry. Here we present an overview of the CHABLIS campaign. We provide details of the measurement location and introduce the Clean Air Sector Laboratory (CASLab) where the majority of the instruments were housed. We describe the meteorological conditions experienced during the campaign and present supporting chemical data, both of which provide a context within which to view the campaign results. Finally we provide a brief summary of highlights from the measurement campaign. Unexpectedly high halogen concentrations profoundly affect the chemistry of many species at Halley throughout the sunlit months, with a secondary role played by emissions from the snowpack. This overarching role for halogens in coastal Antarctic boundary layer chemistry was completely unanticipated, and the results have led to a step-change in our thinking and understanding.

In situ measurements of dimethyl sulphide (DMS) and methane sulphonic acid (MSA) were made at Halley Station, Antarctica (75°35' S, 26°19' W) during February 2004–February 2005 as part of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) project. DMS was present in the atmosphere at Halley all year (average 38.1±43 pptV) with a maximum monthly average value of 113.6±52 pptV in February 2004 coinciding temporally with a minimum in sea extent. Whilst seasonal variability and interannual variability can be attributed to a number of factors, short term variability appeared strongly dependent on air mass origin and trajectory pressure height. The MSA and derived non-sea salt sulphate (nss-SO42−) measurements showed no correlation with those of DMS (regression R2=0.039, and R2=0.001 respectively) in-line with the complexity of DMS fluxes, alternative oxidation routes, transport of air masses and variable spatial coverage of both sea-ice and phytoplankton. MSA was generally low throughout the year, with an annual average of 42 ng m−3 (9.8±13.2 pptV), however MSA: nss-SO42− ratios were high implying a dominance of the addition oxidation route for DMS. Including BrO measurements into MSA production calculations demonstrated the significance of BrO on DMS oxidation within this region of the atmosphere in austral summer. Assuming an 80% yield of DMSO from the reaction of DMS+BrO, an atmospheric concentration of BrO equal to 3 pptV increased the calculated MSA production from DMS by a factor of 9 above that obtained when considering only reaction with the hydroxyl radical. These findings have significant atmospheric implications, but may also impact on the interpretation of ice cores which previously relied on the understanding of MSA and nss-SO42− chemistry to provide information on environmental conditions such as sea ice extent and the origins of sulphur within the ice.