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Global warming is amplified in the Arctic. However, numerical models struggle to represent key processes that determine Arctic weather and climate. To collect data that help to constrain the models, the HALO–(𝒜𝒞)3 aircraft campaign was conducted over the Norwegian and Greenland seas, the Fram Strait, and the central Arctic Ocean in March and April 2022. The campaign focused on one specific challenge posed by the models, namely the reasonable representation of transformations of air masses during their meridional transport into and out of the Arctic via northward moist- and warm-air intrusions (WAIs) and southward marine cold-air outbreaks (CAOs). Observations were made over areas of open ocean, the marginal sea ice zone, and the central Arctic sea ice. Two low-flying and one long-range, high-altitude research aircraft were flown in colocated formation whenever possible. To follow the air mass transformations, a quasi-Lagrangian flight strategy using trajectory calculations was realized, enabling us to sample the same moving-air parcels twice along their trajectories. Seven distinct WAI and 12 CAO cases were probed. From the quasi-Lagrangian measurements, we have quantified the diabatic heating/cooling and moistening/drying of the transported air masses. During CAOs, maximum values of 3 K h−1 warming and 0.3 g kg−1 h−1 moistening were obtained below 1 km altitude. From the observations of WAIs, diabatic cooling rates of up to 0.4 K h−1 and a moisture loss of up to 0.1 g kg−1 h−1 from the ground to about 5.5 km altitude were derived. Furthermore, the development of cloud macrophysical (cloud-top height and horizontal cloud cover) and microphysical (liquid water path, precipitation, and ice index) properties along the southward pathways of the air masses were documented during CAOs, and the moisture budget during a specific WAI event was estimated. In addition, we discuss the statistical frequency of occurrence of the different thermodynamic phases of Arctic low-level clouds, the interaction of Arctic cirrus clouds with sea ice and water vapor, and the characteristics of microphysical and chemical properties of Arctic aerosol particles. Finally, we provide a proof of concept to measure mesoscale divergence and subsidence in the Arctic using data from dropsondes released during the flights.

Using electrochemical gas sensors for quantitative measurements of trace gas components in ambient air introduces several challenges, of which interference, drift and aging of the sensor are the most significant. Frequent and precise calibration as well as thorough characterization of the sensor helps to achieve reliable and repeatable results. We therefore propose the use of a simple, lightweight and inexpensive setup to produce hydrogen calibration gases with precisely known concentrations in ambient air. The hydrogen is produced by electrolysis with electric current monitoring, and the output can be set to any value between ∼ 3 and ∼ 11 µgH2min-1. With a dilution flow of 500 mL min−1, for example, this results in a concentration range from ∼ 70 up to ∼ 240 ppm, but concentrations significantly below or above this range can also be covered with accordingly modified dilution flows. This setup can be used not only for calibration, but also for thorough and long-term characterization of electrochemical gas sensors to evaluate sensitivity, zero voltage and response time over extended periods of time.

Vertical profiles of the mass concentration of black carbon (BC) were measured at altitudes up to 5 km during the PAMARCMiP (Polar Airborne Measurements and Arctic Regional Climate Model simulation Project) aircraft-based field experiment conducted around the northern Greenland Sea (Fram Strait) during March and April 2018 from operation base Station Nord (81.6∘ N, 16.7∘ W). Median BC mass concentrations in individual altitude ranges were 7–18 ng m−3 at standard temperature and pressure at altitudes below 4.5 km. These concentrations were systematically lower than previous observations in the Arctic in spring, conducted by ARCTAS-A in 2008 and NETCARE in 2015, and similar to those observed during HIPPO3 in 2010. Column amounts of BC for altitudes below 5 km in the Arctic (>66.5∘ N; COLBC), observed during the ARCTAS-A and NETCARE experiments, were higher by factors of 4.2 and 2.7, respectively, than those of the PAMARCMiP experiment. These differences could not be explained solely by the different locations of the experiments. The year-to-year variation of COLBC values generally corresponded to that of biomass burning activities in northern midlatitudes over western and eastern Eurasia. Furthermore, numerical model simulations estimated the year-to-year variation of contributions from anthropogenic sources to be smaller than 30 %–40 %. These results suggest that the year-to-year variation of biomass burning activities likely affected BC amounts in the Arctic troposphere in spring, at least in the years examined in this study. The year-to-year variations in BC mass concentrations were also observed at the surface at high Arctic sites Ny-Ålesund and Utqiaġvik (formerly known as Barrow, the location of Barrow Atmospheric Baseline Observatory), although their magnitudes were slightly lower than those in COLBC. Numerical model simulations in general successfully reproduced the observed COLBC values for PAMARCMiP and HIPPO3 (within a factor of 2), whereas they markedly underestimated the values for ARCTAS-A and NETCARE by factors of 3.7–5.8 and 3.3–5.0, respectively. Because anthropogenic contributions account for nearly all of the COLBC (82 %–98 %) in PAMARCMiP and HIPPO3, the good agreement between the observations and calculations for these two experiments suggests that anthropogenic contributions were generally well reproduced. However, the significant underestimations of COLBC for ARCTAS-A and NETCARE suggest that biomass burning contributions were underestimated. In this study, we also investigated plumes with enhanced BC mass concentrations, which were affected by biomass burning emissions, observed at 5 km altitude. Interestingly, the mass-averaged diameter of BC (core) and the shell-to-core diameter ratio of BC-containing particles in the plumes were generally not very different from those in other air samples, which were considered to be mostly aged anthropogenic BC. These observations provide a useful basis to evaluate numerical model simulations of the BC radiative effect in the Arctic region in spring.

Stratospheric inorganic chlorine (Cly) is predominantly released from long-lived chlorinated source gases and, to a small extent, very short-lived chlorinated substances. Cly includes the reservoir species (HCl and ClONO2) and active chlorine species (i.e., ClOx). The active chlorine species drive catalytic cycles that deplete ozone in the polar winter stratosphere. This work presents calculations of inorganic chlorine (Cly) derived from chlorinated source gas measurements on board the High Altitude and Long Range Research Aircraft (HALO) during the Southern Hemisphere Transport, Dynamic and Chemistry (SouthTRAC) campaign in austral late winter and early spring 2019. Results are compared to Cly in the Northern Hemisphere derived from measurements of the POLSTRACC-GW-LCYCLE-SALSA (PGS) campaign in the Arctic winter of 2015/2016. A scaled correlation was used for PGS data, since not all source gases were measured. Using the SouthTRAC data, Cly from a scaled correlation was compared to directly determined Cly and agreed well. An air mass classification based on in situ N2O measurements allocates the measurements to the vortex, the vortex boundary region, and midlatitudes. Although the Antarctic vortex was weakened in 2019 compared to previous years, Cly reached 1687±19 ppt at 385 K; therefore, up to around 50 % of total chlorine was found in inorganic form inside the Antarctic vortex, whereas only 15 % of total chlorine was found in inorganic form in the southern midlatitudes. In contrast, only 40 % of total chlorine was found in inorganic form in the Arctic vortex during PGS, and roughly 20 % was found in inorganic form in the northern midlatitudes. Differences inside the two vortices reach as much as 540 ppt, with more Cly in the Antarctic vortex in 2019 than in the Arctic vortex in 2016 (at comparable distance to the local tropopause). To our knowledge, this is the first comparison of inorganic chlorine within the Antarctic and Arctic polar vortices. Based on the results of these two campaigns, the differences in Cly inside the two vortices are substantial and larger than the inter-annual variations previously reported for the Antarctic.

Aerosol particles impact the Arctic climate system both directly and indirectly by modifying cloud properties, yet our understanding of their vertical distribution, chemical composition, mixing state, and sources in the summertime Arctic is incomplete. In situ vertical observations of particle properties in the high Arctic combined with modelling analysis on source attribution are in short supply, particularly during summer. We thus use airborne measurements of aerosol particle composition to demonstrate the strong contrast between particle sources and composition within and above the summertime Arctic boundary layer. In situ measurements from two complementary aerosol mass spectrometers, the Aircraft-based Laser Ablation Aerosol Mass Spectrometer (ALABAMA) and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), are presented alongside black carbon measurements from an single particle soot photometer (SP2). Particle composition analysis was complemented by trace gas measurements, satellite data, and air mass history modelling to attribute particle properties to particle origin and air mass source regions. Particle composition above the summertime Arctic boundary layer was dominated by chemically aged particles, containing elemental carbon, nitrate, ammonium, sulfate, and organic matter. From our analysis, we conclude that the presence of these particles was driven by transport of aerosol and precursor gases from mid-latitudes to Arctic regions. Specifically, elevated concentrations of nitrate, ammonium, and organic matter coincided with time spent over vegetation fires in northern Canada. In parallel, those particles were largely present in high CO environments (> 90 ppbv). Additionally, we observed that the organic-to-sulfate ratio was enhanced with increasing influence from these fires. Besides vegetation fires, particle sources in mid-latitudes further include anthropogenic emissions in Europe, North America, and East Asia. The presence of particles in the Arctic lower free troposphere, particularly sulfate, correlated with time spent over populated and industrial areas in these regions. Further, the size distribution of free tropospheric particles containing elemental carbon and nitrate was shifted to larger diameters compared to particles present within the boundary layer. Moreover, our analysis suggests that organic matter, when present in the Arctic free troposphere, can partly be identified as low molecular weight dicarboxylic acids (oxalic, malonic, and succinic acid). Particles containing dicarboxylic acids were largely present when the residence time of air masses outside Arctic regions was high. In contrast, particle composition within the marine boundary layer was largely driven by Arctic regional processes. Air mass history modelling demonstrated that alongside primary sea spray particles, marine biogenic sources contributed to secondary aerosol formation via trimethylamine, methanesulfonic acid, sulfate, and other organic species. Our findings improve our knowledge of mid-latitude and Arctic regional sources that influence the vertical distribution of particle chemical composition and mixing state in the Arctic summer.

Despite the potential importance of black carbon (BC) for radiative forcing of the Arctic atmosphere, vertically resolved measurements of the particle light scattering coefficient (σsp) and light absorption coefficient (σap) in the springtime Arctic atmosphere are infrequent, especially measurements at latitudes at or above 80∘ N. Here, relationships among vertically distributed aerosol optical properties (σap, σsp and single scattering albedo or SSA), particle microphysics and particle chemistry are examined for a region of the Canadian archipelago between 79.9 and 83.4∘ N from near the surface to 500 hPa. Airborne data collected during April 2015 are combined with ground-based observations from the observatory at Alert, Nunavut and simulations from the Goddard Earth Observing System (GEOS) model, GEOS-Chem, coupled with the TwO-Moment Aerosol Sectional (TOMAS) model (collectively GEOS-Chem–TOMAS; Kodros et al., 2018) to further our knowledge of the effects of BC on light absorption in the Arctic troposphere. The results are constrained for σsp less than 15 Mm−1, which represent 98 % of the observed σsp, because the single scattering albedo (SSA) has a tendency to be lower at lower σsp, resulting in a larger relative contribution to Arctic warming. At 18.4 m2 g−1, the average BC mass absorption coefficient (MAC) from the combined airborne and Alert observations is substantially higher than the two averaged modelled MAC values (13.6 and 9.1 m2 g−1) for two different internal mixing assumptions, the latter of which is based on previous observations. The higher observed MAC value may be explained by an underestimation of BC, the presence of small amounts of dust and/or possible differences in BC microphysics and morphologies between the observations and model. In comparing the observations and simulations, we present σap and SSA, as measured, and σap∕2 and the corresponding SSA to encompass the lower modelled MAC that is more consistent with accepted MAC values. Median values of the measured σap, rBC and the organic component of particles all increase by a factor of 1.8±0.1, going from near-surface to 750 hPa, and values higher than the surface persist to 600 hPa. Modelled BC, organics and σap agree with the near-surface measurements but do not reproduce the higher values observed between 900 and 600 hPa. The differences between modelled and observed optical properties follow the same trend as the differences between the modelled and observed concentrations of the carbonaceous components (black and organic). Model-observation discrepancies may be mostly due to the modelled ejection of biomass burning particles only into the boundary layer at the sources. For the assumption of the observed MAC value, the SSA range between 0.88 and 0.94, which is significantly lower than other recent estimates for the Arctic, in part reflecting the constraint of σsp Mm−1. The large uncertainties in measuring optical properties and BC, and the large differences between measured and modelled values here and in the literature, argue for improved measurements of BC and light absorption by BC and more vertical profiles of aerosol chemistry, microphysics and other optical properties in the Arctic.

The springtime composition of the Arctic lower troposphere is to a large extent controlled by the transport of midlatitude air masses into the Arctic. In contrast, precipitation and natural sources play the most important role during summer. Within the Arctic region sloping isentropes create a barrier to horizontal transport, known as the polar dome. The polar dome varies in space and time and exhibits a strong influence on the transport of air masses from midlatitudes, enhancing transport during winter and inhibiting transport during summer. We analyzed aircraft-based trace gas measurements in the Arctic from two NETCARE airborne field campaigns (July 2014 and April 2015) with the Alfred Wegener Institute Polar 6 aircraft, covering an area from Spitsbergen to Alaska (134 to 17∘ W and 68 to 83∘ N). Using these data we characterized the transport regimes of midlatitude air masses traveling to the high Arctic based on CO and CO2 measurements as well as kinematic 10 d back trajectories. We found that dynamical isolation of the high Arctic lower troposphere leads to gradients of chemical tracers reflecting different local chemical lifetimes, sources, and sinks. In particular, gradients of CO and CO2 allowed for a trace-gas-based definition of the polar dome boundary for the two measurement periods, which showed pronounced seasonal differences. Rather than a sharp boundary, we derived a transition zone from both campaigns. In July 2014 the polar dome boundary was at 73.5∘ N latitude and 299–303.5 K potential temperature. During April 2015 the polar dome boundary was on average located at 66–68.5∘ N and 283.5–287.5 K. Tracer–tracer scatter plots confirm different air mass properties inside and outside the polar dome in both spring and summer. Further, we explored the processes controlling the recent transport history of air masses within and outside the polar dome. Air masses within the springtime polar dome mainly experienced diabatic cooling while traveling over cold surfaces. In contrast, air masses in the summertime polar dome were diabatically heated due to insolation. During both seasons air masses outside the polar dome slowly descended into the Arctic lower troposphere from above through radiative cooling. Ascent to the middle and upper troposphere mainly took place outside the Arctic, followed by a northward motion. Air masses inside and outside the polar dome were also distinguished by different chemical compositions of both trace gases and aerosol particles. We found that the fraction of amine-containing particles, originating from Arctic marine biogenic sources, is enhanced inside the polar dome. In contrast, concentrations of refractory black carbon are highest outside the polar dome, indicating remote pollution sources. Synoptic-scale weather systems frequently disturb the transport barrier formed by the polar dome and foster exchange between air masses from midlatitudes and polar regions. During the second phase of the NETCARE 2014 measurements a pronounced low-pressure system south of Resolute Bay brought inflow from southern latitudes, which pushed the polar dome northward and significantly affected trace gas mixing ratios in the measurement region. Mean CO mixing ratios increased from 77.9±2.5 to 84.9±4.7 ppbv between these two regimes. At the same time CO2 mixing ratios significantly decreased from 398.16 ± 1.01 to 393.81 ± 2.25 ppmv. Our results demonstrate the utility of applying a tracer-based diagnostic to determine the polar dome boundary for interpreting observations of atmospheric composition in the context of transport history.

The Arctic CLoud Observations Using airborne measurements during polar Day (ACLOUD) campaign was carried out north-west of Svalbard (Norway) between 23 May and 6 June 2017. The objective of ACLOUD was to study Arctic boundary layer and mid-level clouds and their role in Arctic amplification. Two research aircraft (Polar 5 and 6) jointly performed 22 research flights over the transition zone between open ocean and closed sea ice. Both aircraft were equipped with identical instrumentation for measurements of basic meteorological parameters, as well as for turbulent and radiative energy fluxes. In addition, on Polar 5 active and passive remote sensing instruments were installed, while Polar 6 operated in situ instruments to characterize cloud and aerosol particles as well as trace gases. A detailed overview of the specifications, data processing, and data quality is provided here. It is shown that the scientific analysis of the ACLOUD data benefits from the coordinated operation of both aircraft. By combining the cloud remote sensing techniques operated on Polar 5, the synergy of multi-instrument cloud retrieval is illustrated. The remote sensing methods were validated using truly collocated in situ and remote sensing observations. The data of identical instruments operated on both aircraft were merged to extend the spatial coverage of mean atmospheric quantities and turbulent and radiative flux measurement. Therefore, the data set of the ACLOUD campaign provides comprehensive in situ and remote sensing observations characterizing the cloudy Arctic atmosphere. All processed, calibrated, and validated data are published in the World Data Center PANGAEA as instrument-separated data subsets (Ehrlich et al., 2019b, https://doi.org/10.1594/PANGAEA.902603).

Hydrogen peroxide (H2O2) plays a significant role in the oxidizing capacity of the atmosphere. It is an efficient oxidant in the liquid phase and serves as a temporary reservoir for the hydroxyl radical (OH), the most important oxidizing agent in the gas phase. Due to its high solubility, removal of H2O2 due to wet and dry deposition is efficient, being a sink of HOx (OH+HO2) radicals. In the continental boundary layer, the H2O2 budget is controlled by photochemistry, transport and deposition processes. Here we use in situ observations of H2O2 and account for chemical source and removal mechanisms to study the interplay between these processes. The data were obtained during five ground-based field campaigns across Europe from 2008 to 2014 and bring together observations in a boreal forest, two mountainous sites in Germany, and coastal sites in Spain and Cyprus. Most campaigns took place in the summer, while the measurements in the south-west of Spain took place in early winter. Diel variations in H2O2 are strongly site-dependent and indicate a significant altitude dependence. While boundary-layer mixing ratios of H2O2 at low-level sites show classical diel cycles with the lowest values in the early morning and maxima around local noon, diel profiles are reversed on mountainous sites due to transport from the nocturnal residual layer and the free troposphere. The concentration of hydrogen peroxide is largely governed by its main precursor, the hydroperoxy radical (HO2), and shows significant anti-correlation with nitrogen oxides (NOx) that remove HO2. A budget calculation indicates that in all campaigns, the noontime photochemical production rate through the self-reaction of HO2 radicals was much larger than photochemical loss due to reaction with OH and photolysis, and that dry deposition is the dominant loss mechanism. Estimated dry deposition velocities varied between approximately 1 and 6 cm s−1, with relatively high values observed during the day in forested regions, indicating enhanced uptake of H2O2 by vegetation. In order to reproduce the change in H2O2 mixing ratios between sunrise and midday, a variable contribution from transport (10 %–100 %) is required to balance net photochemical production and deposition loss. Transport is most likely related to entrainment from the residual layer above the nocturnal boundary layer during the growth of the boundary layer in the morning.

Motivated by the need to predict how the Arctic atmosphere will change in a warming world, this article summarizes recent advances made by the research consortium NETCARE (Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments) that contribute to our fundamental understanding of Arctic aerosol particles as they relate to climate forcing. The overall goal of NETCARE research has been to use an interdisciplinary approach encompassing extensive field observations and a range of chemical transport, earth system, and biogeochemical models. Several major findings and advances have emerged from NETCARE since its formation in 2013. (1) Unexpectedly high summertime dimethyl sulfide (DMS) levels were identified in ocean water (up to 75 nM) and the overlying atmosphere (up to 1 ppbv) in the Canadian Arctic Archipelago (CAA). Furthermore, melt ponds, which are widely prevalent, were identified as an important DMS source (with DMS concentrations of up to 6 nM and a potential contribution to atmospheric DMS of 20 % in the study area). (2) Evidence of widespread particle nucleation and growth in the marine boundary layer was found in the CAA in the summertime, with these events observed on 41 % of days in a 2016 cruise. As well, at Alert, Nunavut, particles that are newly formed and grown under conditions of minimal anthropogenic influence during the months of July and August are estimated to contribute 20 % to 80 % of the 30–50 nm particle number density. DMS-oxidation-driven nucleation is facilitated by the presence of atmospheric ammonia arising from seabird-colony emissions, and potentially also from coastal regions, tundra, and biomass burning. Via accumulation of secondary organic aerosol (SOA), a significant fraction of the new particles grow to sizes that are active in cloud droplet formation. Although the gaseous precursors to Arctic marine SOA remain poorly defined, the measured levels of common continental SOA precursors (isoprene and monoterpenes) were low, whereas elevated mixing ratios of oxygenated volatile organic compounds (OVOCs) were inferred to arise via processes involving the sea surface microlayer. (3) The variability in the vertical distribution of black carbon (BC) under both springtime Arctic haze and more pristine summertime aerosol conditions was observed. Measured particle size distributions and mixing states were used to constrain, for the first time, calculations of aerosol–climate interactions under Arctic conditions. Aircraft- and ground-based measurements were used to better establish the BC source regions that supply the Arctic via long-range transport mechanisms, with evidence for a dominant springtime contribution from eastern and southern Asia to the middle troposphere, and a major contribution from northern Asia to the surface. (4) Measurements of ice nucleating particles (INPs) in the Arctic indicate that a major source of these particles is mineral dust, likely derived from local sources in the summer and long-range transport in the spring. In addition, INPs are abundant in the sea surface microlayer in the Arctic, and possibly play a role in ice nucleation in the atmosphere when mineral dust concentrations are low. (5) Amongst multiple aerosol components, BC was observed to have the smallest effective deposition velocities to high Arctic snow (0.03 cm s−1).

The vertical distribution of black carbon (BC) particles in the Arctic atmosphere is one of the key parameters controlling their radiative forcing and thus role in Arctic climate change. This work investigates the presence and properties of these light-absorbing aerosols over the High Canadian Arctic (>70∘ N). Airborne campaigns were performed as part of the NETCARE project (Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments) and provided insights into the variability of the vertical distributions of BC particles in summer 2014 and spring 2015. The observation periods covered evolutions of cyclonic disturbances at the polar front, which favoured the transport of air pollution into the High Canadian Arctic, as otherwise this boundary between the air masses largely impedes entrainment of pollution from lower latitudes. A total of 48 vertical profiles of refractory BC (rBC) mass concentration and particle size, extending from 0.1 to 5.5 km altitude were obtained with a Single-Particle Soot Photometer (SP2). Generally, the rBC mass concentration decreased from spring to summer by a factor of 10. Such depletion was associated with a decrease in the mean rBC particle diameter, from approximately 200 to 130 nm at low altitude. Due to the very low number fraction, rBC particles did not substantially contribute to the total aerosol population in summer. The analysis of profiles with potential temperature as vertical coordinate revealed characteristic variability patterns within specific levels of the cold and stably stratified, dome-like, atmosphere over the polar region. The associated history of transport trajectories into each of these levels showed that the variability was induced by changing rates and efficiencies of rBC import. Generally, the source areas affecting the polar dome extended southward with increasing potential temperature (i.e. altitude) level in the dome. While the lower dome was mostly only influenced by low-level transport from sources within the cold central and marginal Arctic, for the mid-dome and upper dome during spring it was found that a cold air outbreak over eastern Europe caused intensified northward transport of air from a corridor over western Russia to central Asia. This sector was affected by emissions from gas flaring, industrial activity and wildfires. The development of transport caused rBC concentrations in the second lowest level to gradually increase from 32 to 49 ng m−3. In the third level this caused the initially low rBC concentration to increase from to 150 ng m−3. A shift in rBC mass-mean diameter, from above 200 nm in the lower polar dome dominated by low-level transport to  nm at higher levels, may indicate that rBC was affected by wet removal mechanisms preferential to larger particle diameters when lifting processes were involved during transport. The summer polar dome had limited exchange with the mid-latitudes. Air pollution was supplied from sources within the marginal Arctic as well as by long-range transport, but in both cases rBC was largely depleted in absolute and relative concentrations. Near the surface, rBC concentrations were  ng m−3, while concentrations increased to  ng m−3 towards the upper boundary of the polar dome. The mass mean particle diameter of 132 nm was smaller than in spring; nonetheless the summer mean mass size distribution resembled the spring distribution from higher levels, with depletion of particles >300 nm. Our work provides vertical, spatial and seasonal information of rBC characteristics in the polar dome over the High Canadian Arctic, offering a more extensive dataset for evaluation of chemical transport models and for radiative forcing assessments than those obtained before by other Arctic aircraft campaigns.

The sources, chemical transformations and removal mechanisms of aerosol transported to the Arctic are key factors that control Arctic aerosol–climate interactions. Our understanding of sources and processes is limited by a lack of vertically resolved observations in remote Arctic regions. We present vertically resolved observations of trace gases and aerosol composition in High Arctic springtime, made largely north of 80° N, during the NETCARE campaign. Trace gas gradients observed on these flights defined the polar dome as north of 66–68° 30′ N and below potential temperatures of 283.5–287.5 K. In the polar dome, we observe evidence for vertically varying source regions and chemical processing. These vertical changes in sources and chemistry lead to systematic variation in aerosol composition as a function of potential temperature. We show evidence for sources of aerosol with higher organic aerosol (OA), ammonium and refractory black carbon (rBC) content in the upper polar dome. Based on FLEXPART-ECMWF calculations, air masses sampled at all levels inside the polar dome (i.e., potential temperature 10 days) in the Arctic, while air masses in the upper polar dome had entered the Arctic more recently. Variations in aerosol composition were closely related to transport history. In the lower polar dome, the measured sub-micron aerosol mass was dominated by sulfate (mean 74 %), with lower contributions from rBC (1 %), ammonium (4 %) and OA (20 %). At higher altitudes and higher potential temperatures, OA, ammonium and rBC contributed 42 %, 8 % and 2 % of aerosol mass, respectively. A qualitative indication for the presence of sea salt showed that sodium chloride contributed to sub-micron aerosol in the lower polar dome, but was not detectable in the upper polar dome. Our observations highlight the differences in Arctic aerosol chemistry observed at surface-based sites and the aerosol transported throughout the depth of the Arctic troposphere in spring.

The two concerted field campaigns, Arctic CLoud Observations Using airborne measurements during polar Day (ACLOUD) and the Physical feedbacks of Arctic planetary boundary level Sea ice, Cloud and AerosoL (PASCAL), took place near Svalbard from 23 May to 26 June 2017. They were focused on studying Arctic mixed-phase clouds and involved observations from two airplanes (ACLOUD), an icebreaker (PASCAL) and a tethered balloon, as well as ground-based stations. Here, we present the synoptic development during the 35-day period of the campaigns, using near-surface and upper-air meteorological observations, as well as operational satellite, analysis, and reanalysis data. Over the campaign period, short-term synoptic variability was substantial, dominating over the seasonal cycle. During the first campaign week, cold and dry Arctic air from the north persisted, with a distinct but seasonally unusual cold air outbreak. Cloudy conditions with mostly low-level clouds prevailed. The subsequent 2 weeks were characterized by warm and moist maritime air from the south and east, which included two events of warm air advection. These synoptical disturbances caused lower cloud cover fractions and higher-reaching cloud systems. In the final 2 weeks, adiabatically warmed air from the west dominated, with cloud properties strongly varying within the range of the two other periods. Results presented here provide synoptic information needed to analyze and interpret data of upcoming studies from ACLOUD/PASCAL, while also offering unprecedented measurements in a sparsely observed region.

Within the framework of the RACEPAC (Radiation–Aerosol–Cloud Experiment in the Arctic Circle) project, the Arctic aerosol, arriving at a ground-based station in Tuktoyaktuk (Mackenzie River delta area, Canada), was characterized during a period of 3 weeks in May 2014. Basic meteorological parameters and particle number size distributions (PNSDs) were observed and two distinct types of air masses were found. One type were typical Arctic haze air masses, termed accumulation-type air masses, characterized by a monomodal PNSD with a pronounced accumulation mode at sizes above 100 nm. These air masses were observed during a period when back trajectories indicate an air mass origin in the north-east of Canada. The other air mass type is characterized by a bimodal PNSD with a clear minimum around 90 nm and with an Aitken mode consisting of freshly formed aerosol particles. Back trajectories indicate that these air masses, termed Aitken-type air masses, originated from the North Pacific. In addition, the application of the PSCF receptor model shows that air masses with their origin in active fire areas in central Canada and Siberia, in areas of industrial anthropogenic pollution (Norilsk and Prudhoe Bay Oil Field) and the north-west Pacific have enhanced total particle number concentrations (NCN). Generally, NCN ranged from 20 to 500 cm−3, while cloud condensation nuclei (CCN) number concentrations were found to cover a range from less than 10 up to 250 cm−3 for a supersaturation (SS) between 0.1 and 0.7 %. The hygroscopicity parameter κ of the CCN was determined to be 0.23 on average and variations in κ were largely attributed to measurement uncertainties. Furthermore, simultaneous PNSD measurements at the ground station and on the Polar 6 research aircraft were performed. We found a good agreement of ground-based PNSDs with those measured between 200 and 1200 m. During two of the four overflights, particle number concentrations at 3000 m were found to be up to 20 times higher than those measured below 2000 m; for one of these two flights, PNSDs measured above 2000 m showed a different shape than those measured at lower altitudes. This is indicative of long-range transport from lower latitudes into the Arctic that can advect aerosol from different regions in different heights.

Long-range transport of aerosol from lower latitudes to the high Arctic may be a significant contributor to climate forcing in the Arctic. To identify the sources of key contaminants entering the Canadian High Arctic an intensive campaign of snow sampling was completed at Alert, Nunavut, from September 2014 to June 2015. Fresh snow samples collected every few days were analyzed for black carbon, major ions, and metals, and this rich data set provided an opportunity for a temporally refined source apportionment of snow composition via positive matrix factorization (PMF) in conjunction with FLEXPART (FLEXible PARTicle dispersion model) potential emission sensitivity analysis. Seven source factors were identified: sea salt, crustal metals, black carbon, carboxylic acids, nitrate, non-crustal metals, and sulfate. The sea salt and crustal factors showed good agreement with expected composition and primarily northern sources. High loadings of V and Se onto Factor 2, crustal metals, was consistent with expected elemental ratios, implying these metals were not primarily anthropogenic in origin. Factor 3, black carbon, was an acidic factor dominated by black carbon but with some sulfate contribution over the winter-haze season. The lack of K+ associated with this factor, a Eurasian source, and limited known forest fire events coincident with this factor's peak suggested a predominantly anthropogenic combustion source. Factor 4, carboxylic acids, was dominated by formate and acetate with a moderate correlation to available sunlight and an oceanic and North American source. A robust identification of this factor was not possible; however, atmospheric photochemical reactions, ocean microlayer reaction, and biomass burning were explored as potential contributors. Factor 5, nitrate, was an acidic factor dominated by NO3−, with a likely Eurasian source and mid-winter peak. The isolation of NO3− on a separate factor may reflect its complex atmospheric processing, though the associated source region suggests possibly anthropogenic precursors. Factor 6, non-crustal metals, showed heightened loadings of Sb, Pb, and As, and correlation with other metals traditionally associated with industrial activities. Similar to Factor 3 and 5, this factor appeared to be largely Eurasian in origin. Factor 7, sulfate, was dominated by SO42− and MS with a fall peak and high acidity. Coincident volcanic activity and northern source regions may suggest a processed SO2 source of this factor.

The source strength and capability of aerosol particles in the Arctic to act as cloud condensation nuclei have important implications for understanding the indirect aerosol–cloud effect within the polar climate system. It has been shown in several Arctic regions that ultrafine particle (UFP) formation and growth is a key contributor to aerosol number concentrations during the summer. This study uses aerosol number size distribution measurements from shipboard expeditions aboard the research icebreaker CCGS Amundsen in the summers of 2014 and 2016 throughout the Canadian Arctic to gain a deeper understanding of the drivers of UFP formation and growth within this marine boundary layer. UFP number concentrations (diameter > 4 nm) in the range of 101–104 cm−3 were observed during the two seasons, with concentrations greater than 103 cm−3 occurring more frequently in 2016. Higher concentrations in 2016 were associated with UFP formation and growth, with events occurring on 41 % of days, while events were only observed on 6 % of days in 2014. Assessment of relevant parameters for aerosol nucleation showed that the median condensation sink in this region was approximately 1.2 h−1 in 2016 and 2.2 h−1 in 2014, which lie at the lower end of ranges observed at even the most remote stations reported in the literature. Apparent growth rates of all observed events in both expeditions averaged 4.3 ± 4.1 nm h−1, in general agreement with other recent studies at similar latitudes. Higher solar radiation, lower cloud fractions, and lower sea ice concentrations combined with differences in the developmental stage and activity of marine microbial communities within the Canadian Arctic were documented and help explain differences between the aerosol measurements made during the 2014 and 2016 expeditions. These findings help to motivate further studies of biosphere–atmosphere interactions within the Arctic marine environment to explain the production of UFP and their growth to sizes relevant for cloud droplet activation.

Size-resolved and vertical profile measurements of single particle chemical composition (sampling altitude range 50–3000 m) were conducted in July 2014 in the Canadian high Arctic during an aircraft-based measurement campaign (NETCARE 2014). We deployed the single particle laser ablation aerosol mass spectrometer ALABAMA (vacuum aerodynamic diameter range approximately 200–1000 nm) to identify different particle types and their mixing states. On the basis of the single particle analysis, we found that a significant fraction (23 %) of all analyzed particles (in total: 7412) contained trimethylamine (TMA). Two main pieces of evidence suggest that these TMA-containing particles originated from emissions within the Arctic boundary layer. First, the maximum fraction of particulate TMA occurred in the Arctic boundary layer. Second, compared to particles observed aloft, TMA particles were smaller and less oxidized. Further, air mass history analysis, associated wind data and comparison with measurements of methanesulfonic acid give evidence of a marine-biogenic influence on particulate TMA. Moreover, the external mixture of TMA-containing particles and sodium and chloride (Na ∕ Cl-) containing particles, together with low wind speeds, suggests particulate TMA results from secondary conversion of precursor gases released by the ocean. In contrast to TMA-containing particles originating from inner-Arctic sources, particles with biomass burning markers (such as levoglucosan and potassium) showed a higher fraction at higher altitudes, indicating long-range transport as their source. Our measurements highlight the importance of natural, marine inner-Arctic sources for composition and growth of summertime Arctic aerosol.

Deep convection is an efficient mechanism for vertical trace gas transport from Earth's surface to the upper troposphere (UT). The convective redistribution of short-lived trace gases emitted at the surface typically results in a C-shaped profile. This redistribution mechanism can impact photochemical processes, e.g. ozone and radical production in the UT on a large scale due to the generally longer lifetimes of species like formaldehyde (HCHO) and hydrogen peroxide (H2O2), which are important HOx precursors (HOx = OH + HO2 radicals). Due to the solubility of HCHO and H2O2 their transport may be suppressed as they are efficiently removed by wet deposition. Here we present a case study of deep convection over Germany in the summer of 2007 within the framework of the HOOVER II project. Airborne in situ measurements within the in- and outflow regions of an isolated thunderstorm provide a unique data set to study the influence of deep convection on the transport efficiency of soluble and insoluble trace gases. Comparing the in- and outflow indicates an almost undiluted transport of insoluble trace gases from the boundary layer to the UT. The ratios of out : inflow of CO and CH4 are 0.94 ± 0.04 and 0.99 ± 0.01, respectively. For the soluble species HCHO and H2O2 these ratios are 0.55 ± 0.09 and 0.61 ± 0.08, respectively, indicating partial scavenging and washout. Chemical box model simulations show that post-convection secondary formation of HCHO and H2O2 cannot explain their enhancement in the UT. A plausible explanation, in particular for the enhancement of the highly soluble H2O2, is degassing from cloud droplets during freezing, which reduces the retention coefficient.

Ozone (O3) is an important atmospheric oxidant, a greenhouse gas, and a hazard to human health and agriculture. Here we describe airborne in situ measurements and model simulations of O3 and its precursors during tropical and extratropical field campaigns over South America and Europe, respectively. Using the measurements, net ozone formation/destruction tendencies are calculated and compared to 3-D chemistry–transport model simulations. In general, observation-based net ozone tendencies are positive in the continental boundary layer and the upper troposphere at altitudes above ∼ 6 km in both environments. On the other hand, in the marine boundary layer and the middle troposphere, from the top of the boundary layer to about 6–8 km altitude, net O3 destruction prevails. The ozone tendencies are controlled by ambient concentrations of nitrogen oxides (NOx). In regions with net ozone destruction the available NOx is below the threshold value at which production and destruction of O3 balance. While threshold NO values increase with altitude, in the upper troposphere NOx concentrations are generally higher due to the integral effect of convective precursor transport from the boundary layer, downward transport from the stratosphere and NOx produced by lightning. Two case studies indicate that in fresh convective outflow of electrified thunderstorms net ozone production is enhanced by a factor 5–6 compared to the undisturbed upper tropospheric background. The chemistry–transport model MATCH-MPIC generally reproduces the pattern of observation-based net ozone tendencies but mostly underestimates the magnitude of the net tendency (for both net ozone production and destruction).

In this study 1 year of ceilometer measurements taken in the Kathmandu Valley, Nepal, in the framework of the SusKat project (A Sustainable Atmosphere for the Kathmandu Valley) were analysed to investigate the diurnal variation of the mixing layer height (MLH) and its dependency on the meteorological conditions. In addition, the impact of the MLH on the temporal variation and the magnitude of the measured black carbon concentrations are analysed for each season. Based on the assumption that black carbon aerosols are vertically well mixed within the mixing layer and the finding that the mixing layer varies only little during night time and morning hours, black carbon emission fluxes are estimated for these hours and per month. Even though this method is relatively simple, it can give an observationally based first estimate of the black carbon emissions in this region, especially illuminating the seasonal cycle of the emission fluxes. The monthly minimum median MLH values typically range between 150 and 200 m during night and early morning hours, the monthly maximum median values between 625 m in July and 1460 m in March. Seasonal differences are not only found in the absolute MLHs, but also in the duration of the typical daytime maximum ranging between 2 and 3 h in January and 6–7 h in May. During the monsoon season a diurnal cycle has been observed with the smallest amplitude (typically between 400 and 500 m), with the lowest daytime mixing height of all seasons (maximum monthly median values typically between 600 and 800 m), and also the highest night-time and early morning mixing height of all seasons (minimum monthly median values typically between 200 and 220 m). These characteristics can mainly be explained with the frequently present clouds and the associated reduction in incoming solar radiation and outgoing longwave radiation. In general, the black carbon concentrations show a clear anticorrelation with MLH measurements, although this relation is less pronounced in the monsoon season. The daily evolution of the black carbon diurnal cycle differs between the seasons, partly due to the different meteorological conditions including the MLH. Other important reasons are the different main emission sources and their diurnal variations in the individual seasons. The estimation of the black carbon emission flux for the morning hours show a clear seasonal cycle with maximum values in December to April. Compared to the emission flux values provided by different emission databases for this region, the estimated values here are considerably higher. Several possible sources of uncertainty are considered, and even the absolute lower bound of the emissions based on our methodology is higher than in most emissions datasets, providing strong evidence that the black carbon emissions for this region have likely been underestimated in modelling studies thus far.

Vertical distributions of atmospheric dimethyl sulfide (DMS(g)) were sampled aboard the research aircraft Polar 6 near Lancaster Sound, Nunavut, Canada, in July 2014 and on pan-Arctic flights in April 2015 that started from Longyearbyen, Spitzbergen, and passed through Alert and Eureka, Nunavut, and Inuvik, Northwest Territories. Larger mean DMS(g) mixing ratios were present during April 2015 (campaign mean of 116 ± 8 pptv) compared to July 2014 (campaign mean of 20 ± 6 pptv). During July 2014, the largest mixing ratios were found near the surface over the ice edge and open water. DMS(g) mixing ratios decreased with altitude up to about 3 km. During April 2015, profiles of DMS(g) were more uniform with height and some profiles showed an increase with altitude. DMS reached as high as 100 pptv near 2500 m. Relative to the observation averages, GEOS-Chem (www.geos-chem.org) chemical transport model simulations were higher during July and lower during April. Based on the simulations, more than 90 % of the July DMS(g) below 2 km and more than 90 % of the April DMS(g) originated from Arctic seawater (north of 66° N). During April, 60 % of the DMS(g), between 500 and 3000 m originated from Arctic seawater. During July 2014, FLEXPART (FLEXible PARTicle dispersion model) simulations locate the sampled air mass over Baffin Bay and the Canadian Arctic Archipelago 4 days back from the observations. During April 2015, the locations of the air masses 4 days back from sampling were varied: Baffin Bay/Canadian Archipelago, the Arctic Ocean, Greenland and the Pacific Ocean. Our results highlight the role of open water below the flight as the source of DMS(g) during July 2014 and the influence of long-range transport (LRT) of DMS(g) from further afield in the Arctic above 2500 m during April 2015.

We present in situ measurements of the trace gas composition of the upper tropospheric (UT) Asian summer monsoon anticyclone (ASMA) performed with the High Altitude and Long Range Research Aircraft (HALO) in the frame of the Earth System Model Validation (ESMVal) campaign. Air masses with enhanced O3 mixing ratios were encountered after entering the ASMA at its southern edge at about 150 hPa on 18 September 2012. This is in contrast to the presumption that the anticyclone's interior is dominated by recently uplifted air with low O3 in the monsoon season. We also observed enhanced CO and HCl in the ASMA, which are tracers for boundary layer pollution and tropopause layer (TL) air or stratospheric in-mixing respectively. In addition, reactive nitrogen was enhanced in the ASMA. Along the HALO flight track across the ASMA boundary, strong gradients of these tracers separate anticyclonic from outside air. Lagrangian trajectory calculations using HYSPLIT show that HALO sampled a filament of UT air three times, which included air masses uplifted from the lower or mid-troposphere north of the Bay of Bengal. The trace gas gradients between UT and uplifted air masses were preserved during transport within a belt of streamlines fringing the central part of the anticyclone (fringe), but are smaller than the gradients across the ASMA boundary. Our data represent the first in situ observations across the southern part and downstream of the eastern ASMA flank. Back-trajectories starting at the flight track furthermore indicate that HALO transected the ASMA where it was just splitting into a Tibetan and an Iranian part. The O3-rich filament is diverted from the fringe towards the interior of the original anticyclone, and is at least partially bound to become part of the new Iranian eddy. A simulation with the ECHAM/MESSy Atmospheric Chemistry (EMAC) model is found to reproduce the observations reasonably well. It shows that O3-rich air is entrained by the outer streamlines of the anticyclone at its eastern flank. Back-trajectories and increased HCl mixing ratios indicate that the entrained air originates in the stratospherically influenced TL. Photochemical ageing of air masses in the ASMA additionally increases O3 in originally O3-poor, but CO-rich air. Simulated monthly mean trace gas distributions show decreased O3 in the ASMA centre only at the 100 hPa level in July and August, but at lower altitudes and in September the ASMA is dominated by increased O3. The combination of entrainment from the tropopause region, photochemistry and dynamical instabilities can explain the in situ observations, and might have a larger impact on the highly variable trace gas composition of the anticyclone than previously thought.

Rapidly rising temperatures and loss of snow and ice cover have demonstrated the unique vulnerability of the high Arctic to climate change. There are major uncertainties in modelling the chemical depositional and scavenging processes of Arctic snow. To that end, fresh snow samples collected on average every 4 days at Alert, Nunavut, from September 2014 to June 2015 were analyzed for black carbon, major ions, and metals, and their concentrations and fluxes were reported. Comparison with simultaneous measurements of atmospheric aerosol mass loadings yields effective deposition velocities that encompass all processes by which the atmospheric species are transferred to the snow. It is inferred from these values that dry deposition is the dominant removal mechanism for several compounds over the winter while wet deposition increased in importance in the fall and spring, possibly due to enhanced scavenging by mixed-phase clouds. Black carbon aerosol was the least efficiently deposited species to the snow.

Motivated by increasing levels of open ocean in the Arctic summer and the lack of prior altitude-resolved studies, extensive aerosol measurements were made during 11 flights of the NETCARE July 2014 airborne campaign from Resolute Bay, Nunavut. Flights included vertical profiles (60 to 3000 m above ground level) over open ocean, fast ice, and boundary layer clouds and fogs. A general conclusion, from observations of particle numbers between 5 and 20 nm in diameter (N5 − 20), is that ultrafine particle formation occurs readily in the Canadian high Arctic marine boundary layer, especially just above ocean and clouds, reaching values of a few thousand particles cm−3. By contrast, ultrafine particle concentrations are much lower in the free troposphere. Elevated levels of larger particles (for example, from 20 to 40 nm in size, N20 − 40) are sometimes associated with high N5 − 20, especially over low clouds, suggestive of aerosol growth. The number densities of particles greater than 40 nm in diameter (N > 40) are relatively depleted at the lowest altitudes, indicative of depositional processes that will lower the condensation sink and promote new particle formation. The number of cloud condensation nuclei (CCN; measured at 0.6 % supersaturation) are positively correlated with the numbers of small particles (down to roughly 30 nm), indicating that some fraction of these newly formed particles are capable of being involved in cloud activation. Given that the summertime marine Arctic is a biologically active region, it is important to better establish the links between emissions from the ocean and the formation and growth of ultrafine particles within this rapidly changing environment.

Global simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) using artificial tracers of air mass origin are used to analyze transport mechanisms from the Asian monsoon region into the lower stratosphere. In a case study, the transport of air masses from the Asian monsoon anticyclone originating in India/China by an eastward-migrating anticyclone which broke off from the main anticyclone on 20 September 2012 and filaments separated at the northeastern flank of the anticyclone are analyzed. Enhanced contributions of young air masses (younger than 5 months) are found within the separated anticyclone confined at the top by the thermal tropopause. Further, these air masses are confined by the anticyclonic circulation and, on the polar side, by the subtropical jet such that the vertical structure resembles a bubble within the upper troposphere. Subsequently, these air masses are transported eastwards along the subtropical jet and enter the lower stratosphere by quasi-horizontal transport in a region of double tropopauses most likely associated with Rossby wave breaking events. As a result, thin filaments with enhanced signatures of tropospheric trace gases were measured in the lower stratosphere over Europe during the TACTS/ESMVal campaign in September 2012 in very good agreement with CLaMS simulations. Our simulations demonstrate that source regions in Asia and in the Pacific Ocean have a significant impact on the chemical composition of the lower stratosphere of the Northern Hemisphere. Young, moist air masses, in particular at the end of the monsoon season in September/October 2012, flooded the extratropical lower stratosphere in the Northern Hemisphere with contributions of up to ≈ 30 % at 380 K (with the remaining fraction being aged air). In contrast, the contribution of young air masses to the Southern Hemisphere is much lower. At the end of October 2012, approximately 1.5 ppmv H2O is found in the lower Northern Hemisphere stratosphere (at 380 K) from source regions both in Asia and in the tropical Pacific compared to a mean water vapor content of ≈ 5 ppmv. In addition to this main transport pathway from the Asian monsoon anticyclone to the east along the subtropical jet and subsequent transport into the northern lower stratosphere, a second horizontal transport pathway out of the anticyclone to the west into the tropics (TTL) is found in agreement with MIPAS HCFC-22 measurements.

The first airborne measurements of the Far-InfraRed Radiometer (FIRR) were performed in April 2015 during the panarctic NETCARE campaign. Vertical profiles of spectral upwelling radiance in the range 8–50 µm were measured in clear and cloudy conditions from the surface up to 6 km. The clear sky profiles highlight the strong dependence of radiative fluxes to the temperature inversion typical of the Arctic. Measurements acquired for total column water vapour from 1.5 to 10.5 mm also underline the sensitivity of the far-infrared greenhouse effect to specific humidity. The cloudy cases show that optically thin ice clouds increase the cooling rate of the atmosphere, making them important pieces of the Arctic energy balance. One such cloud exhibited a very complex spatial structure, characterized by large horizontal heterogeneities at the kilometre scale. This emphasizes the difficulty of obtaining representative cloud observations with airborne measurements but also points out how challenging it is to model polar clouds radiative effects. These radiance measurements were successfully compared to simulations, suggesting that state-of-the-art radiative transfer models are suited to study the cold and dry Arctic atmosphere. Although FIRR in situ performances compare well to its laboratory performances, complementary simulations show that upgrading the FIRR radiometric resolution would greatly increase its sensitivity to atmospheric and cloud properties. Improved instrument temperature stability in flight and expected technological progress should help meet this objective. The campaign overall highlights the potential for airborne far-infrared radiometry and constitutes a relevant reference for future similar studies dedicated to the Arctic and for the development of spaceborne instruments.

Observations addressing effects of aerosol particles on summertime Arctic clouds are limited. An airborne study, carried out during July 2014 from Resolute Bay, Nunavut, Canada, as part of the Canadian NETCARE project, provides a comprehensive in situ look into some effects of aerosol particles on liquid clouds in the clean environment of the Arctic summer. Median cloud droplet number concentrations (CDNC) from 62 cloud samples are 10 cm−3 for low-altitude cloud (clouds topped below 200 m) and 101 cm−3 for higher-altitude cloud (clouds based above 200 m). The lower activation size of aerosol particles is ≤ 50 nm diameter in about 40 % of the cases. Particles as small as 20 nm activated in the higher-altitude clouds consistent with higher supersaturations (S) for those clouds inferred from comparison of the CDNC with cloud condensation nucleus (CCN) measurements. Over 60 % of the low-altitude cloud samples fall into the CCN-limited regime of Mauritsen et al. (2011), within which increases in CDNC may increase liquid water and warm the surface. These first observations of that CCN-limited regime indicate a positive association of the liquid water content (LWC) and CDNC, but no association of either the CDNC or LWC with aerosol variations. Above the Mauritsen limit, where aerosol indirect cooling may result, changes in particles with diameters from 20 to 100 nm exert a relatively strong influence on the CDNC. Within this exceedingly clean environment, as defined by low carbon monoxide and low concentrations of larger particles, the background CDNC are estimated to range between 16 and 160 cm−3, where higher values are due to activation of particles ≤ 50 nm that likely derive from natural sources. These observations offer the first wide-ranging reference for the aerosol cloud albedo effect in the summertime Arctic.

The transport of air masses originating from the Asian monsoon anticyclone into the extratropical upper troposphere and lower stratosphere (Ex-UTLS) above potential temperatures Θ = 380 K was identified during the HALO aircraft mission TACTS in August and September 2012. In situ measurements of CO, O3 and N2O during TACTS flight 2 on 30 August 2012 show the irreversible mixing of aged stratospheric air masses with younger (recently transported from the troposphere) ones within the Ex-UTLS. Backward trajectories calculated with the trajectory module of CLaMS indicate that these tropospherically affected air masses originate from the Asian monsoon anticyclone. These air masses are subsequently transported above potential temperatures Θ = 380 K from the monsoon circulation region into the Ex-UTLS, where they subsequently mix with stratospheric air masses. The overall trace gas distribution measured during TACTS shows that this transport pathway had affected the chemical composition of the Ex-UTLS during boreal summer and autumn 2012. This leads to an intensification of the tropospheric influence on the extratropical lower stratosphere with PV > 8 pvu within 3 weeks during the TACTS mission. During the same time period a weakening of the tropospheric influence on the lowermost stratosphere (LMS) is determined. The study shows that the transport of air masses originating from the Asian summer monsoon region within the lower stratosphere affects the change in the chemical composition of the Ex-UTLS over Europe and thus contributes to the flushing of the LMS during summer 2012.

The summertime Arctic lower troposphere is a relatively pristine background aerosol environment dominated by nucleation and Aitken mode particles. Understanding the mechanisms that control the formation and growth of aerosol is crucial for our ability to predict cloud properties and therefore radiative balance and climate. We present an analysis of an aerosol growth event observed in the Canadian Arctic Archipelago during summer as part of the NETCARE project. Under stable and clean atmospheric conditions, with low inversion heights, carbon monoxide less than 80 ppbv, and black carbon less than 5 ng m−3, we observe growth of small particles, −3. Results from this case study highlight the potential importance of secondary organic aerosol formation and its role in growing nucleation mode aerosol into CCN-active sizes in this remote marine environment.

Decreasing sea ice and increasing marine navigability in northern latitudes have changed Arctic ship traffic patterns in recent years and are predicted to increase annual ship traffic in the Arctic in the future. Development of effective regulations to manage environmental impacts of shipping requires an understanding of ship emissions and atmospheric processing in the Arctic environment. As part of the summer 2014 NETCARE (Network on Climate and Aerosols) campaign, the plume dispersion and gas and particle emission factors of effluents originating from the Canadian Coast Guard icebreaker Amundsen operating near Resolute Bay, NU, Canada, were investigated. The Amundsen burned distillate fuel with 1.5 wt % sulfur. Emissions were studied via plume intercepts using the Polar 6 aircraft measurements, an analytical plume dispersion model, and using the FLEXPART-WRF Lagrangian particle dispersion model. The first plume intercept by the research aircraft was carried out on 19 July 2014 during the operation of the Amundsen in the open water. The second and third plume intercepts were carried out on 20 and 21 July 2014 when the Amundsen had reached the ice edge and operated under ice-breaking conditions. Typical of Arctic marine navigation, the engine load was low compared to cruising conditions for all of the plume intercepts. The measured species included mixing ratios of CO2, NOx, CO, SO2, particle number concentration (CN), refractory black carbon (rBC), and cloud condensation nuclei (CCN). The results were compared to similar experimental studies in mid-latitudes. Plume expansion rates (γ) were calculated using the analytical model and found to be γ = 0.75 ± 0.81, 0.93 ± 0.37, and 1.19 ± 0.39 for plumes 1, 2, and 3, respectively. These rates were smaller than prior studies conducted at mid-latitudes, likely due to polar boundary layer dynamics, including reduced turbulent mixing compared to mid-latitudes. All emission factors were in agreement with prior observations at low engine loads in mid-latitudes. Ice-breaking increased the NOx emission factor from EFNOx = 43.1 ± 15.2 to 71.6 ± 9.68 and 71.4 ± 4.14 g kg-diesel−1 for plumes 1, 2, and 3, likely due to changes in combustion temperatures. The CO emission factor was EFCO = 137 ± 120, 12.5 ± 3.70 and 8.13 ± 1.34 g kg-diesel−1 for plumes 1, 2, and 3. The rBC emission factor was EFrBC = 0.202 ± 0.052 and 0.202 ± 0.125 g kg-diesel−1 for plumes 1 and 2. The CN emission factor was reduced while ice-breaking from EFCN = 2.41 ± 0.47 to 0.45 ± 0.082 and 0.507 ± 0.037 × 1016 kg-diesel−1 for plumes 1, 2, and 3. At 0.6 % supersaturation, the CCN emission factor was comparable to observations in mid-latitudes at low engine loads with EFCCN = 3.03 ± 0.933, 1.39 ± 0.319, and 0.650 ± 0.136 × 1014 kg-diesel−1 for plumes 1, 2, and 3.

This study presents the analysis of the structure and air mass characteristics of the lower atmosphere during the field campaign PARADE (PArticles and RAdicals: Diel observations of the impact of urban and biogenic Emissions) on Mount Kleiner Feldberg in southwestern Germany during late summer 2011. We analysed measurements of meteorological variables (temperature, moisture, pressure, wind speed and direction) from radio soundings and of chemical tracers (carbon dioxide, ozone) from aircraft measurements. We focus on the thermodynamic and dynamic properties that control the chemical distribution of atmospheric constituents in the boundary layer. We show that the evolution of tracer profiles of CO2 and O3 indicate mixing across the inversion layer (or entrainment zone). This finding is supported by the analysis of tracer–tracer correlations which are indicative for mixing and the relation of tracer profiles in relation to the evolution of the boundary layer height deduced from radio soundings. The study shows the relevance of entrainment processes for the lower troposphere in general and specifically that the tracer–tracer correlation method can be used to identify mixing and irreversible exchange processes across the inversion layer.

Dehydration in the Antarctic winter stratosphere is a well-known phenomenon that is annually observed by satellites and occasionally observed by balloon-borne measurements. However, in situ measurements of dehydrated air masses in the Antarctic vortex are very rare. Here, we present detailed observations with the in situ and GLORIA remote sensing instrument payload aboard the German aircraft HALO. Strongly dehydrated air masses down to 1.6 ppmv of water vapor were observed as far north as 47° S in an altitude between 12 and 13 km in the lowermost stratosphere. The dehydration can be traced back to individual ice formation events above the Antarctic Peninsula and Plateau, where ice crystals sedimented out and water vapor was irreversibly removed. Within these dehydrated stratospheric air masses, filaments of moister air reaching down to the tropopause are detected with the high-resolution limb sounder, GLORIA. Furthermore, dehydrated air masses are observed with GLORIA in the Antarctic lowermost stratosphere down to 7 km. With the help of a backward trajectory analysis, a midlatitude origin of the moist filaments in the vortex can be identified, while the dry air masses down to 7 km have stratospheric origins. Antarctic stratosphere–troposphere exchange (STE) and transport of dehydrated air masses into the troposphere are investigated. Further, it is shown that the exchange process can be attributed to several successive Rossby wave events in combination with an isentropic exchange of air masses across the thermal tropopause. The transport into the troposphere is caused by air masses that are detached from the potential vorticity (PV) structure by Rossby wave breaking events and subsequently transported diabatically across the dynamical tropopause. Once transported to the troposphere, air masses with stratospheric origin can reach near-surface levels within several days.

Convective redistribution of ozone and its precursors between the boundary layer (BL) and the free troposphere (FT) influences photochemistry, in particular in the middle and upper troposphere (UT). We present a case study of convective transport during the GABRIEL campaign over the tropical rain forest in Suriname in October 2005. During one measurement flight the inflow and outflow regions of a cumulonimbus cloud (Cb) have been characterized. We identified a distinct layer between 9 and 11 km altitude with enhanced mixing ratios of CO, O3, HOx, acetone and acetonitrile. The elevated O3 contradicts the expectation that convective transport brings low-ozone air from the boundary layer to the outflow region. Entrainment of ozone-rich air is estimated to account for 62% (range: 33–91%) of the observed O3. Ozone is enhanced by only 5–6% by photochemical production in the outflow due to enhanced NO from lightning, based on model calculations using observations including the first reported HOx measurements over the tropical rainforest. The "excess" ozone in the outflow is most probably due to direct production by corona discharge associated with lightning. We deduce a production rate of 5.12 × 1028 molecules O3 flash−1 (range: 9.89 × 1026–9.82 × 1028 molecules O3 flash−1), which is at the upper limit of the range reported previously.

In situ airborne measurements of OH and HO2 with the HORUS (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy) instrument were performed in the summertime upper troposphere across Europe during the HOOVER 2 (HOx OVer EuRope) campaign in July 2007. Complementary measurements of trace gas species and photolysis frequencies were conducted to obtain a broad data set, which has been used to quantify the significant HOx sources and sinks. In this study we compare the in situ measurement of OH and HO2 with simulated mixing ratios from the constrained box model CAABA/MECCA (Chemistry As A Box Model Application/Module Efficiently Calculating the Chemistry of the Atmosphere), and the global circulation model EMAC (ECHAM5/MESSy Atmospheric Chemistry Model). The constrained box model reproduces the observed OH and HO2 mixing ratios with better agreement (obs/mod median 98% OH, 96% HO2) than the global model (median 76% OH, 59% HO2). The observations and the computed HOx sources and sinks are used to identify deviations between the models and their impacts on the calculated HOx budget.

Peroxy radicals were measured by a PeRCA (Peroxy Radical Chemical Amplifier) instrument in the boundary layer during the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) campaign at a coastal, forested site influenced by urban-industrial emissions in southern Spain in late autumn. Total peroxy radicals (RO2* = HO2 + ΣRO2) generally showed a daylight maximum between 10 and 50 pptv at 13:00 UTC, with an average of 18 pptv over the 15 days of measurements. Emissions from the industrial area of Huelva often impacted the measurement site at night during the campaign. The processing of significant levels of anthropogenic organics leads to an intense nocturnal radical chemistry accompanied by formation of organic peroxy radicals at comparable levels to those of summer photochemical conditions with peak events up to 60–80 pptv. The RO2 production initiated by reactions of NO3 with organic trace gases was estimated to be significant, but not sufficient to account for the concentrations of RO2* observed in air masses carrying high pollutant loading. The nocturnal production of peroxy radicals in those periods seems therefore to be dominated by ozonolysis of volatile organic compounds, in particular alkenes of industrial petrochemical origin. RO2* diurnal variations were consistent with HO2 measurements available at the site. HO2/RO2* ratios generally varied between 0.3 and 0.6, though on some occasions this ratio was likely to have been affected by instrumental artifacts (overestimated HO2) associated with high RO2 loads.

Abstract The Arctic is a sentinel of global change. This region is influenced by multiple physical and socio-economic drivers and feedbacks, impacting both the natural and human environment. Air pollution is one such driver that impacts Arctic climate change, ecosystems and health but significant uncertainties still surround quantification of these effects. Arctic air pollution includes harmful trace gases (e.g. tropospheric ozone) and particles (e.g. black carbon, sulphate) and toxic substances (e.g. polycyclic aromatic hydrocarbons) that can be transported to the Arctic from emission sources located far outside the region, or emitted within the Arctic from activities including shipping, power production, and other industrial activities. This paper qualitatively summarizes the complex science issues motivating the creation of a new international initiative, PACES (air Pollution in the Arctic: Climate, Environment and Societies). Approaches for coordinated, international and interdisciplinary research on this topic are described with the goal to improve predictive capability via new understanding about sources, processes, feedbacks and impacts of Arctic air pollution. Overarching research actions are outlined, in which we describe our recommendations for 1) the development of trans-disciplinary approaches combining social and economic research with investigation of the chemical and physical aspects of Arctic air pollution; 2) increasing the quality and quantity of observations in the Arctic using long-term monitoring and intensive field studies, both at the surface and throughout the troposphere; and 3) developing improved predictive capability across a range of spatial and temporal scales.

Ambient total OH reactivity was measured at the Finnish boreal forest station SMEAR II in Hyytiälä (Latitude 61°51' N; Longitude 24°17' E) in July and August 2010 using the Comparative Reactivity Method (CRM). The CRM – total OH reactivity method – is a direct, in-situ determination of the total loss rate of hydroxyl radicals (OH) caused by all reactive species in air. During the intensive field campaign HUMPPA-COPEC 2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) the total OH reactivity was monitored both inside (18 m) and directly above the forest canopy (24 m) for the first time. The comparison between these two total OH reactivity measurements, absolute values and the temporal variation have been analyzed here. Stable boundary layer conditions during night and turbulent mixing in the daytime induced low and high short-term variability, respectively. The impact on total OH reactivity from biogenic emissions and associated photochemical products was measured under "normal" and "stressed" (i.e. prolonged high temperature) conditions. The advection of biomass burning emissions to the site caused a marked change in the total OH reactivity vertical profile. By comparing the OH reactivity contribution from individually measured compounds and the directly measured total OH reactivity, the size of any unaccounted for or "missing" sink can be deduced for various atmospheric influences. For "normal" boreal conditions a missing OH reactivity of 58%, whereas for "stressed" boreal conditions a missing OH reactivity of 89% was determined. Various sources of not quantified OH reactive species are proposed as possible explanation for the high missing OH reactivity.

In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3–40.5 s−1), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7–23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was ~18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.

We study the interactions between atmospheric boundary layer (ABL) dynamics and atmospheric chemistry using a mixed-layer model coupled to chemical reaction schemes. Guided by both atmospheric and chemical measurements obtained during the DOMINO (Diel Oxidant Mechanisms in relation to Nitrogen Oxides) campaign (2008), numerical experiments are performed to study the role of ABL dynamics and the accuracy of chemical schemes with different complexity: the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) and a reduced mechanism of this chemical system. Both schemes produce satisfactory results, indicating that the reduced scheme is capable of reproducing the O3-NOx-VOC-HOx diurnal cycle during conditions characterized by a low NOx regime and small O3 tendencies (less than 1 ppb per hour). By focusing on the budget equations of chemical species in the mixed-layer model, we show that for species like O3, NO and NO2, the influence of entrainment and boundary layer growth is of the same order as chemical production/loss. This indicates that an accurate representation of ABL processes is crucial in understanding the diel cycle of chemical species. By comparing the time scales of chemical reactive species with the mixing time scale of turbulence, we propose a classification based on the Damköhler number to further determine the importance of dynamics on chemistry during field campaigns. Our findings advocate an integrated approach, simultaneously solving the ABL dynamics and chemical reactions, in order to obtain a better understanding of chemical pathways and processes and the interpretation of the results obtained during measurement campaigns.

Nighttime mixing ratios of boundary layer N2O5 were determined using cavity-ring-down spectroscopy during the DOMINO campaign in Southern Spain (Diel Oxidant Mechanisms In relation to Nitrogen Oxides, 21 November 2008–8 December 2008). N2O5 mixing ratios ranged from below the detection limit (~5 ppt) to ~500 ppt. A steady-state analysis constrained by measured mixing ratios of N2O5, NO2 and O3 was used to derive NO3 lifetimes and compare them to calculated rates of loss via gas-phase and heterogeneous reactions of both NO3 and N2O5. Three distinct types of air masses were encountered, which were largely marine (Atlantic), continental or urban-industrial in origin. NO3 lifetimes were longest in the Atlantic sector (up to ~30 min) but were very short (a few seconds) in polluted, air masses from the local city and petroleum-related industrial complex of Huelva. Air from the continental sector was an intermediate case. The high reactivity to NO3 of the urban air mass was not accounted for by gas-phase and heterogeneous reactions, rates of which were constrained by measurements of NO, volatile organic species and aerosol surface area. In general, high NO2 mixing ratios were associated with low NO3 lifetimes, though heterogeneous processes (e.g. reaction of N2O5 on aerosol) were generally less important than direct gas-phase losses of NO3. The presence of SO2 at levels above ~2 ppb in the urban air sector was always associated with very low N2O5 mixing ratios indicating either very short NO3 lifetimes in the presence of combustion-related emissions or an important role for reduced sulphur species in urban, nighttime chemistry. High production rates coupled with low lifetimes of NO3 imply an important contribution of nighttime chemistry to removal of both NOx and VOC.

This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiälä, Finland from 12 July–12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urban anthropogenic pollution (pentane and SO2) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures.

During the DOMINO (Diel Oxidant Mechanism In relation to Nitrogen Oxides) campaign in southwest Spain we measured simultaneously all quantities necessary to calculate a photostationary state for HONO in the gas phase. These quantities comprise the concentrations of OH, NO, and HONO and the photolysis frequency of NO2, j(NO2) as a proxy for j(HONO). This allowed us to calculate values of the unknown HONO daytime source. This unknown HONO source, normalized by NO2 mixing ratios and expressed as a conversion frequency (% h−1), showed a clear dependence on j(NO2) with values up to 43% h−1 at noon. We compared our unknown HONO source with values calculated from the measured field data for two recently proposed processes, the light-induced NO2 conversion on soot surfaces and the reaction of electronically excited NO2* with water vapour, with the result that these two reactions normally contributed less than 10% (2 + soot + hν; and 2* + H2O) to our unknown HONO daytime source. OH production from HONO photolysis was found to be larger (by 20%) than the "classical" OH formation from ozone photolysis (O(1D)) integrated over the day.

In this study we report measurements of hydrogen peroxide (H2O2), methyl hydroperoxide* (MHP* as a proxy of MHP based on an unspecific measurement of total organic peroxides) and formaldehyde (HCHO) from the HOx OVer EuRope (HOOVER) project (HOx = OH+HO2). HOOVER included two airborne field campaigns, in October 2006 and July 2007. Measurement flights were conducted from the base of operation Hohn (Germany, 54° N, 9° E) towards the Mediterranean and to the subpolar regions over Norway. We find negative concentration gradients with increasing latitude throughout the troposphere for H2O2 and CH3OOH*. In contrast, observed HCHO is almost homogeneously distributed over central and northern Europe and is elevated over the Mediterranean. In general, the measured gradients tend to be steepest entering the Mediterranean region, where we also find the highest abundances of the 3 species. Mixing ratios of these tracers generally decrease with altitude. H2O2 and CH3OOH* show maxima above the boundary layer at 2–5 km, being more distinct over southern than over northern Europe. We also present a comparison of our data with simulations by two global 3-D-models, MATCH-MPIC and EMAC, and with the box model CAABA. The models realistically represent altitude and latitude gradients for both HCHO and hydroperoxides (ROOH). In contrast, the models have problems reproducing the absolute mixing ratios, in particular of H2O2. Large uncertainties about retention coefficients and cloud microphysical parameters suggest that cloud scavenging might be a large source of error for the simulation of H2O2. A sensitivity study with EMAC shows a strong influence of cloud and precipitation scavenging on the budget of H2O2 as simulations improve significantly with this effect switched off.

As a major source region of the hydroxyl radical OH, the Tropics largely control the oxidation capacity of the atmosphere on a global scale. However, emissions of hydrocarbons from the tropical rainforest that react rapidly with OH can potentially deplete the amount of OH and thereby reduce the oxidation capacity. The airborne GABRIEL field campaign in equatorial South America (Suriname) in October 2005 investigated the influence of the tropical rainforest on the HOx budget (HOx = OH + HO2). The first observations of OH and HO2 over a tropical rainforest are compared to steady state concentrations calculated with the atmospheric chemistry box model MECCA. The important precursors and sinks for HOx chemistry, measured during the campaign, are used as constraining parameters for the simulation of OH and HO2. Significant underestimations of HOx are found by the model over land during the afternoon, with mean ratios of observation to model of 12.2 ± 3.5 and 4.1 ± 1.4 for OH and HO2, respectively. The discrepancy between measurements and simulation results is correlated to the abundance of isoprene. While for low isoprene mixing ratios (above ocean or at altitudes >3 km), observation and simulation agree fairly well, for mixing ratios >200 pptV (x observations as a function of isoprene. Box model simulations have been performed with the condensed chemical mechanism of MECCA and with the detailed isoprene reaction scheme of MCM, resulting in similar results for HOx concentrations. Simulations with constrained HO2 concentrations show that the conversion from HO2 to OH in the model is too low. However, by neglecting the isoprene chemistry in the model, observations and simulations agree much better. An OH source similar to the strength of the OH sink via isoprene chemistry is needed in the model to resolve the discrepancy. A possible explanation is that the oxidation of isoprene by OH not only dominates the removal of OH but also produces it in a similar amount. Several additional reactions which directly produce OH have been implemented into the box model, suggesting that upper limits in producing OH are still not able to reproduce the observations (improvement by factors of ≈2.4 and ≈2 for OH and HO2, respectively). We determine that OH has to be recycled to 94% instead of the simulated 38% to match the observations, which is most likely to happen in the isoprene degradation process, otherwise additional sources are required.

Direct measurements of OH and HO2 over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy), adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO2 mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO2 were encountered in the boundary layer over the rainforest. The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurement-derived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission.

We present a comparison of different Lagrangian and chemical box model calculations with measurement data obtained during the GABRIEL campaign over the tropical Atlantic Ocean and the Amazon rainforest in the Guyanas, October 2005. Lagrangian modelling of boundary layer (BL) air constrained by measurements is used to derive a horizontal gradient (≈5.6 pmol/mol km−1) of CO from the ocean to the rainforest (east to west). This is significantly smaller than that derived from the measurements (16–48 pmol/mol km−1), indicating that photochemical production from organic precursors alone cannot explain the observed strong gradient. It appears that HCHO is overestimated by the Lagrangian and chemical box models, which include dry deposition but not exchange with the free troposphere (FT). The relatively short lifetime of HCHO implies substantial BL-FT exchange. The mixing-in of FT air affected by African and South American biomass burning at an estimated rate of 0.12 h−1 increases the CO and decreases the HCHO mixing ratios, improving agreement with measurements. A mean deposition velocity of 1.35 cm/s for H2O2 over the ocean as well as over the rainforest is deduced assuming BL-FT exchange adequate to the results for CO. The measured increase of the organic peroxides from the ocean to the rainforest (≈0.66 nmol/mol d−1) is significantly overestimated by the Lagrangian model, even when using high values for the deposition velocity and the entrainment rate. Our results point at either heterogeneous loss of organic peroxides and/or their radical precursors, underestimated photodissociation or missing reaction paths of peroxy radicals not forming peroxides in isoprene chemistry. We calculate a mean integrated daytime net ozone production (NOP) in the BL of (0.2±5.9) nmol/mol (ocean) and (2.4±2.1) nmol/mol (rainforest). The NOP strongly correlates with NO and has a positive tendency in the boundary layer over the rainforest.