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Elongated open-water areas in sea ice (leads) release sea spray particles to the atmosphere. However, there is limited knowledge on the amount, properties and drivers of sea spray emitted from leads, and no existing parameterization of this process is available for use in models. In this work, we use measurements of aerosol fluxes from Nilsson et al. (2001) to produce an estimate of the location, timing and amount of sea spray emissions from leads at the scale of the Arctic Ocean for 1 year. Lead fractions are derived using sea ice data sets from numerical models and satellite detection. The proposed parameterization estimates that leads account for 0.3 %–9.8 % of the annual sea salt aerosol number emissions in the Arctic Ocean regions where sea ice concentration is greater than 80 %. Assuming similar size distributions to those from emissions from the open ocean, leads account for 30 %–85 % of mass emissions in sea ice regions. The total annual mass of sea salt emitted from leads, 0.1–2.1 Tg yr−1, is comparable to the mass of sea salt aerosol transported above sea ice from the open ocean, according to the MERRA-2 reanalysis. In addition to providing the first estimates of possible upper and lower bounds of sea spray emissions from leads, the conceptual model developed in this work is implemented and tested in the regional atmospheric chemistry model WRF-Chem. Given the estimates obtained in this work, the impact of sea spray from leads on Arctic clouds and radiative budget needs to be further explored.

Reactive halogens play a prominent role in the atmospheric chemistry of the Arctic during springtime. Field measurements and modeling studies suggest that halogens are emitted into the atmosphere from snowpack and reactions on wind-blown snow-sourced aerosols. The relative importance of snowpack and blowing snow sources is still debated, both at local scales and regionally throughout the Arctic. To understand the implications of these halogen sources on a pan-Arctic scale, we simulate Arctic reactive bromine chemistry in the atmospheric chemical transport model GEOS-Chem. Two mechanisms are included: (1) a blowing snow sea salt aerosol formation mechanism and (2) a snowpack mechanism assuming uniform molecular bromine production from all snow surfaces. We compare simulations including neither mechanism, each mechanism individually, and both mechanisms to examine conditions where one process may dominate or the mechanisms may interact. We compare the models using these mechanisms to observations of bromine monoxide (BrO) derived from multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instruments on O-Buoy platforms on the sea ice and at a coastal site in Utqiaġvik, Alaska, during spring 2015. Model estimations of hourly and monthly average BrO are improved by assuming a constant yield of 0.1 % molecular bromine from all snowpack surfaces on ozone deposition. The blowing snow aerosol mechanism increases modeled BrO by providing more bromide-rich aerosol surface area for reactive bromine recycling. The snowpack mechanism led to increased model BrO across the Arctic Ocean with maximum production in coastal regions, whereas the blowing snow aerosol mechanism increases BrO in specific areas due to high surface wind speeds. Our uniform snowpack source has a greater impact on BrO mixing ratios than the blowing snow source. Model results best replicate several features of BrO observations during spring 2015 when using both mechanisms in conjunction, adding evidence that these mechanisms are both active during the Arctic spring. Extending our transport model throughout the entire year leads to predictions of enhanced fall BrO that are not supported by observations.

Microplastics are found in the environment globally, but their atmospheric transport is not well understood. Here the authors report atmospheric microplastic pollution at the Pic du Midi Observatory, suggesting free long range transport in the troposphere.

The role of polar regions is increasing in terms of megatrends such as globalization, new transport routes, demography, and the use of natural resources with consequent effects on regional and transported pollutant concentrations. We set up the ERA-PLANET Strand 4 project “iCUPE – integrative and Comprehensive Understanding on Polar Environments” to provide novel insights and observational data on global grand challenges with an Arctic focus. We utilize an integrated approach combining in situ observations, satellite remote sensing Earth observations (EOs), and multi-scale modeling to synthesize data from comprehensive long-term measurements, intensive campaigns, and satellites to deliver data products, metrics, and indicators to stakeholders concerning the environmental status, availability, and extraction of natural resources in the polar areas. The iCUPE work consists of thematic state-of-the-art research and the provision of novel data in atmospheric pollution, local sources and transboundary transport, the characterization of arctic surfaces and their changes, an assessment of the concentrations and impacts of heavy metals and persistent organic pollutants and their cycling, the quantification of emissions from natural resource extraction, and the validation and optimization of satellite Earth observation (EO) data streams. In this paper we introduce the iCUPE project and summarize initial results arising out of the integration of comprehensive in situ observations, satellite remote sensing, and multi-scale modeling in the Arctic context.

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).

Ice nucleating particles (INPs) in the Arctic can influence climate and precipitation in the region; yet our understanding of the concentrations and sources of INPs in this region remain uncertain. In the following, we (1) measured concentrations of INPs in the immersion mode in the Canadian Arctic marine boundary layer during summer 2014 on board the CCGS Amundsen, (2) determined ratios of surface areas of mineral dust aerosol to sea spray aerosol, and (3) investigated the source region of the INPs using particle dispersion modelling. Average concentrations of INPs at −15, −20, and −25 ∘C were 0.005, 0.044, and 0.154 L−1, respectively. These concentrations fall within the range of INP concentrations measured in other marine environments. For the samples investigated the ratio of mineral dust surface area to sea spray surface area ranged from 0.03 to 0.09. Based on these ratios and the ice active surface site densities of mineral dust and sea spray aerosol determined in previous laboratory studies, our results suggest that mineral dust is a more important contributor to the INP population than sea spray aerosol for the samples analysed. Based on particle dispersion modelling, the highest concentrations of INPs were often associated with lower-latitude source regions such as the Hudson Bay area, eastern Greenland, or north-western continental Canada. On the other hand, the lowest concentrations were often associated with regions further north of the sampling sites and over Baffin Bay. A weak correlation was observed between INP concentrations and the time the air mass spent over bare land, and a weak negative correlation was observed between INP concentrations and the time the air mass spent over ice and open water. These combined results suggest that mineral dust from local sources is an important contributor to the INP population in the Canadian Arctic marine boundary layer during summer 2014.

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain–Fritsch + Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.

During the ACCESS airborne campaign in July 2012, extensive boreal forest fires resulted in significant aerosol transport to the Arctic. A 10-day episode combining intense biomass burning over Siberia and low-pressure systems over the Arctic Ocean resulted in efficient transport of plumes containing black carbon (BC) towards the Arctic, mostly in the upper troposphere (6–8 km). A combination of in situ observations (DLR Falcon aircraft), satellite analysis and WRF-Chem simulations is used to understand the vertical and horizontal transport mechanisms of BC with a focus on the role of wet removal. Between the northwestern Norwegian coast and the Svalbard archipelago, the Falcon aircraft sampled plumes with enhanced CO concentrations up to 200 ppbv and BC mixing ratios up to 25 ng kg−1. During transport to the Arctic region, a large fraction of BC particles are scavenged by two wet deposition processes, namely wet removal by large-scale precipitation and removal in wet convective updrafts, with both processes contributing almost equally to the total accumulated deposition of BC. Our results underline that applying a finer horizontal resolution (40 instead of 100 km) improves the model performance, as it significantly reduces the overestimation of BC levels observed at a coarser resolution in the mid-troposphere. According to the simulations at 40 km, the transport efficiency of BC (TEBC) in biomass burning plumes was larger (60 %), because it was impacted by small accumulated precipitation along trajectory (1 mm). In contrast TEBC was small (BC due to large-scale precipitation is responsible for a sharp meridional gradient in the distribution of BC concentrations. Wet removal in cumulus clouds is the cause of modeled vertical gradient of TEBC, especially in the mid-latitudes, reflecting the distribution of convective precipitation, but is dominated in the Arctic region by the large-scale wet removal associated with the formation of stratocumulus clouds in the planetary boundary layer (PBL) that produce frequent drizzle.

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.

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.

During the 2008 International Polar Year, the POLARCAT (Polar Study using Aircraft, Remote Sensing, Surface Measurements, and Models of Climate Chemistry, Aerosols, and Transport) campaign, conducted in summer over Greenland and Canada, produced a large number of measurements from three aircraft and seven ozonesonde stations. Here we present an observation-integrated analysis based on three different types of O3 measurements: airborne lidar, airborne UV absorption or chemiluminescence measurement, and intensified electrochemical concentration cell (ECC) ozonesonde profiles. Discussion of the latitudinal and vertical variability of tropospheric ozone north of 55° N during this period is performed with the aid of a regional model (WFR-Chem). The model is able to reproduce the O3 latitudinal and vertical variability but with a negative O3 bias of 6–15 ppbv in the free troposphere above 4 km, especially over Canada. For Canada, large average CO concentrations in the free troposphere above 4 km ( > 130 ppbv) and the weak correlation (3 and PV suggest that stratosphere–troposphere exchange (STE) is not the major contributor to average tropospheric ozone at latitudes less than 70° N, due to the fact that local biomass burning (BB) emissions were significant during the 2008 summer period. Conversely, significant STE is found over Greenland according to the better O3 vs. PV correlation ( > 40 %) and the higher values of the 75th PV percentile. It is related to the persistence of cyclonic activity during the summer over Baffin Bay. Using differences between average concentration above Northern and Southern Canada, a weak negative latitudinal summer ozone gradient of −6 to −8 ppbv is found in the mid-troposphere between 4 and 8 km. This is attributed to an efficient O3 photochemical production from BB emissions at latitudes less than 65° N, while the STE contribution is more homogeneous in the latitude range 55–70° N. A positive ozone latitudinal gradient of 12 ppbv is observed in the same altitude range over Greenland not because of an increasing latitudinal influence of STE, but because of different long-range transport from multiple mid-latitude sources (North America, Europe, and even Asia for latitudes higher than 77° N). For the Arctic latitudes (> 80° N), free tropospheric O3 concentrations during summer 2008 are related to a mixture of Asian pollution and stratospheric O3 transport across the tropopause.

The ability of seven state-of-the-art chemistry–aerosol models to reproduce distributions of tropospheric ozone and its precursors, as well as aerosols over eastern Asia in summer 2008, is evaluated. The study focuses on the performance of models used to assess impacts of pollutants on climate and air quality as part of the EU ECLIPSE project. Models, run using the same ECLIPSE emissions, are compared over different spatial scales to in situ surface, vertical profiles and satellite data. Several rather clear biases are found between model results and observations, including overestimation of ozone at rural locations downwind of the main emission regions in China, as well as downwind over the Pacific. Several models produce too much ozone over polluted regions, which is then transported downwind. Analysis points to different factors related to the ability of models to simulate VOC-limited regimes over polluted regions and NOx limited regimes downwind. This may also be linked to biases compared to satellite NO2, indicating overestimation of NO2 over and to the north of the northern China Plain emission region. On the other hand, model NO2 is too low to the south and west of this region and over South Korea/Japan. Overestimation of ozone is linked to systematic underestimation of CO particularly at rural sites and downwind of the main Chinese emission regions. This is likely to be due to enhanced destruction of CO by OH. Overestimation of Asian ozone and its transport downwind implies that radiative forcing from this source may be overestimated. Model-observation discrepancies over Beijing do not appear to be due to emission controls linked to the Olympic Games in summer 2008.With regard to aerosols, most models reproduce the satellite-derived AOD patterns over eastern China. Our study nevertheless reveals an overestimation of ECLIPSE model mean surface BC and sulphate aerosols in urban China in summer 2008. The effect of the short-term emission mitigation in Beijing is too weak to explain the differences between the models. Our results rather point to an overestimation of SO2 emissions, in particular, close to the surface in Chinese urban areas. However, we also identify a clear underestimation of aerosol concentrations over northern India, suggesting that the rapid recent growth of emissions in India, as well as their spatial extension, is underestimated in emission inventories. Model deficiencies in the representation of pollution accumulation due to the Indian monsoon may also be playing a role. Comparison with vertical aerosol lidar measurements highlights a general underestimation of scattering aerosols in the boundary layer associated with overestimation in the free troposphere pointing to modelled aerosol lifetimes that are too long. This is likely linked to too strong vertical transport and/or insufficient deposition efficiency during transport or export from the boundary layer, rather than chemical processing (in the case of sulphate aerosols). Underestimation of sulphate in the boundary layer implies potentially large errors in simulated aerosol–cloud interactions, via impacts on boundary-layer clouds.This evaluation has important implications for accurate assessment of air pollutants on regional air quality and global climate based on global model calculations. Ideally, models should be run at higher resolution over source regions to better simulate urban–rural pollutant gradients and/or chemical regimes, and also to better resolve pollutant processing and loss by wet deposition as well as vertical transport. Discrepancies in vertical distributions require further quantification and improvement since these are a key factor in the determination of radiative forcing from short-lived pollutants.

Dimethyl sulfide (DMS) plays a major role in the global sulfur cycle. In addition, its atmospheric oxidation products contribute to the formation and growth of atmospheric aerosol particles, thereby influencing cloud condensation nuclei (CCN) populations and thus cloud formation. The pristine summertime Arctic atmosphere is strongly influenced by DMS. However, atmospheric DMS mixing ratios have only rarely been measured in the summertime Arctic. During July–August, 2014, we conducted the first high time resolution (10 Hz) DMS mixing ratio measurements for the eastern Canadian Archipelago and Baffin Bay as one component of the Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments (NETCARE). DMS mixing ratios ranged from below the detection limit of 4 to 1155 pptv (median 186 pptv) during the 21-day shipboard campaign. A transfer velocity parameterization from the literature coupled with coincident atmospheric and seawater DMS measurements yielded air–sea DMS flux estimates ranging from 0.02 to 12 µmol m−2 d−1. Air-mass trajectory analysis using FLEXPART-WRF and sensitivity simulations with the GEOS-Chem chemical transport model indicated that local sources (Lancaster Sound and Baffin Bay) were the dominant contributors to the DMS measured along the 21-day ship track, with episodic transport from the Hudson Bay System. After adjusting GEOS-Chem oceanic DMS values in the region to match measurements, GEOS-Chem reproduced the major features of the measured time series but was biased low overall (2–1006 pptv, median 72 pptv), although within the range of uncertainty of the seawater DMS source. However, during some 1–2 day periods the model underpredicted the measurements by more than an order of magnitude. Sensitivity tests indicated that non-marine sources (lakes, biomass burning, melt ponds, and coastal tundra) could make additional episodic contributions to atmospheric DMS in the study region, although local marine sources of DMS dominated. Our results highlight the need for both atmospheric and seawater DMS data sets with greater spatial and temporal resolution, combined with further investigation of non-marine DMS sources for the Arctic.

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.

Size-segregated aerosol sulfate concentrations were measured on board the Canadian Coast Guard Ship (CCGS) Amundsen in the Arctic during July 2014. The objective of this study was to utilize the isotopic composition of sulfate to address the contribution of anthropogenic and biogenic sources of aerosols to the growth of the different aerosol size fractions in the Arctic atmosphere. Non-sea-salt sulfate is divided into biogenic and anthropogenic sulfate using stable isotope apportionment techniques. A considerable amount of the average sulfate concentration in the fine aerosols with a diameter 63 %), which is higher than in previous Arctic studies measuring above the ocean during fall ( 30 %) (Norman et al., 1999). The anthropogenic sulfate concentration was less than that of biogenic sulfate, with potential sources being long-range transport and, more locally, the Amundsen's emissions. Despite attempts to minimize the influence of ship stack emissions, evidence from larger-sized particles demonstrates a contribution from local pollution. A comparison of δ34S values for SO2 and fine aerosols was used to show that gas-to-particle conversion likely occurred during most sampling periods. δ34S values for SO2 and fine aerosols were similar, suggesting the same source for SO2 and aerosol sulfate, except for two samples with a relatively high anthropogenic fraction in particles 2 emphasize the role of marine organisms (e.g., phytoplankton, algae, bacteria) in the formation of fine particles above the Arctic Ocean during the productive summer months.

Continuous hourly measurements of gas-phase ammonia (NH3(g)) were taken from 13 July to 7 August 2014 on a research cruise throughout Baffin Bay and the eastern Canadian Arctic Archipelago. Concentrations ranged from 30 to 650 ng m−3 (40–870 pptv) with the highest values recorded in Lancaster Sound (74°13′ N, 84°00′ W). Simultaneous measurements of total ammonium ([NHx]), pH and temperature in the ocean and in melt ponds were used to compute the compensation point (χ), which is the ambient NH3(g) concentration at which surface–air fluxes change direction. Ambient NH3(g) was usually several orders of magnitude larger than both χocean and χMP (3) indicating these surface pools are net sinks of NH3. Flux calculations estimate average net downward fluxes of 1.4 and 1.1 ng m−2 s−1 for the open ocean and melt ponds, respectively. Sufficient NH3(g) was present to neutralize non-sea-salt sulfate (nss-SO42−) in the boundary layer during most of the study. This finding was corroborated with a historical data set of PM2.5 composition from Alert, Nunavut (82°30′ N, 62°20′ W) wherein the median ratio of NH4+/nss-SO42− equivalents was greater than 0.75 in June, July and August. The GEOS-Chem chemical transport model was employed to examine the impact of NH3(g) emissions from seabird guano on boundary-layer composition and nss-SO42− neutralization. A GEOS-Chem simulation without seabird emissions underestimated boundary layer NH3(g) by several orders of magnitude and yielded highly acidic aerosol. A simulation that included seabird NH3 emissions was in better agreement with observations for both NH3(g) concentrations and nss-SO42− neutralization. This is strong evidence that seabird colonies are significant sources of NH3 in the summertime Arctic, and are ubiquitous enough to impact atmospheric composition across the entire Baffin Bay region. Large wildfires in the Northwest Territories were likely an important source of NH3, but their influence was probably limited to the Central Canadian Arctic. Implications of seabird-derived N-deposition to terrestrial and aquatic ecosystems are also discussed.

In this study, we quantify the impacts of shipping pollution on air quality and shortwave radiative effect in northern Norway, using WRF-Chem (Weather Research and Forecasting with chemistry) simulations combined with high-resolution, real-time STEAM2 (Ship Traffic Emissions Assessment Model version 2) shipping emissions. STEAM2 emissions are evaluated using airborne measurements from the ACCESS (Arctic Climate Change, Economy and Society) aircraft campaign, which was conducted in the summer 2012, in two ways. First, emissions of nitrogen oxides (NOx) and sulfur dioxide (SO2) are derived for specific ships by combining in situ measurements in ship plumes and FLEXPART-WRF plume dispersion modeling, and these values are compared to STEAM2 emissions for the same ships. Second, regional WRF-Chem runs with and without STEAM2 ship emissions are performed at two different resolutions, 3 km × 3 km and 15 km × 15 km, and evaluated against measurements along flight tracks and average campaign profiles in the marine boundary layer and lower troposphere. These comparisons show that differences between STEAM2 emissions and calculated emissions can be quite large (−57 to +148 %) for individual ships, but that WRF-Chem simulations using STEAM2 emissions reproduce well the average NOx, SO2 and O3 measured during ACCESS flights. The same WRF-Chem simulations show that the magnitude of NOx and ozone (O3) production from ship emissions at the surface is not very sensitive (10 particulate matter enhancements due to ships are moderately sensitive (15 %) to resolution. The 15 km resolution WRF-Chem simulations are used to estimate the regional impacts of shipping pollution in northern Norway. Our results indicate that ship emissions are an important source of pollution along the Norwegian coast, enhancing 15-day-averaged surface concentrations of NOx ( ∼ +80 %), SO2 ( ∼ +80 %), O3 ( ∼ +5 %), black carbon ( ∼ +40 %), and PM2.5 ( ∼ +10 %). The residence time of black carbon originating from shipping emissions is 1.4 days. Over the same 15-day period, ship emissions in northern Norway have a global shortwave (direct + semi-direct + indirect) radiative effect of −9.3 m Wm−2.

A model intercomparison activity was inspired by the large suite of observations of atmospheric composition made during the International Polar Year (2008) in the Arctic. Nine global and two regional chemical transport models participated in this intercomparison and performed simulations for 2008 using a common emissions inventory to assess the differences in model chemistry and transport schemes. This paper summarizes the models and compares their simulations of ozone and its precursors and presents an evaluation of the simulations using a variety of surface, balloon, aircraft and satellite observations. Each type of measurement has some limitations in spatial or temporal coverage or in composition, but together they assist in quantifying the limitations of the models in the Arctic and surrounding regions. Despite using the same emissions, large differences are seen among the models. The cloud fields and photolysis rates are shown to vary greatly among the models, indicating one source of the differences in the simulated chemical species. The largest differences among models, and between models and observations, are in NOy partitioning (PAN vs. HNO3) and in oxygenated volatile organic compounds (VOCs) such as acetaldehyde and acetone. Comparisons to surface site measurements of ethane and propane indicate that the emissions of these species are significantly underestimated. Satellite observations of NO2 from the OMI (Ozone Monitoring Instrument) have been used to evaluate the models over source regions, indicating anthropogenic emissions are underestimated in East Asia, but fire emissions are generally overestimated. The emission factors for wildfires in Canada are evaluated using the correlations of VOCs to CO in the model output in comparison to enhancement factors derived from aircraft observations, showing reasonable agreement for methanol and acetaldehyde but underestimate ethanol, propane and acetone, while overestimating ethane emission factors.

We have evaluated tropospheric ozone enhancement in air dominated by biomass burning emissions at high latitudes (> 50° N) in July 2008, using 10 global chemical transport model simulations from the POLMIP multi-model comparison exercise. In model air masses dominated by fire emissions, ΔO3/ΔCO values ranged between 0.039 and 0.196 ppbv ppbv−1 (mean: 0.113 ppbv ppbv−1) in freshly fire-influenced air, and between 0.140 and 0.261 ppbv ppbv−1 (mean: 0.193 ppbv) in more aged fire-influenced air. These values are in broad agreement with the range of observational estimates from the literature. Model ΔPAN/ΔCO enhancement ratios show distinct groupings according to the meteorological data used to drive the models. ECMWF-forced models produce larger ΔPAN/ΔCO values (4.47 to 7.00 pptv ppbv−1) than GEOS5-forced models (1.87 to 3.28 pptv ppbv−1), which we show is likely linked to differences in efficiency of vertical transport during poleward export from mid-latitude source regions. Simulations of a large plume of biomass burning and anthropogenic emissions exported from towards the Arctic using a Lagrangian chemical transport model show that 4-day net ozone change in the plume is sensitive to differences in plume chemical composition and plume vertical position among the POLMIP models. In particular, Arctic ozone evolution in the plume is highly sensitive to initial concentrations of PAN, as well as oxygenated VOCs (acetone, acetaldehyde), due to their role in producing the peroxyacetyl radical PAN precursor. Vertical displacement is also important due to its effects on the stability of PAN, and subsequent effect on NOx abundance. In plumes where net ozone production is limited, we find that the lifetime of ozone in the plume is sensitive to hydrogen peroxide loading, due to the production of HOx from peroxide photolysis, and the key role of HO2 + O3 in controlling ozone loss. Overall, our results suggest that emissions from biomass burning lead to large-scale photochemical enhancement in high-latitude tropospheric ozone during summer.

During the POLARCAT-France airborne campaign in April 2008, pollution originating from anthropogenic and biomass burning emissions was measured in the European Arctic. We compare these aircraft measurements with simulations using the WRF-Chem model to investigate model representation of aerosols transported from Europe to the Arctic. Modeled PM2.5 is evaluated using European Monitoring and Evaluation Programme (EMEP) measurements in source regions and POLARCAT aircraft measurements in the Scandinavian Arctic. Total PM2.5 agrees well with the measurements, although the model overestimates nitrate and underestimates organic carbon in source regions. Using WRF-Chem in combination with the Lagrangian model FLEXPART-WRF, we find that during the campaign the research aircraft sampled two different types of European plumes: mixed anthropogenic and fire plumes from eastern Europe and Russia transported below 2 km, and anthropogenic plumes from central Europe uplifted by warm conveyor belt circulations to 5–6 km. Both modeled plume types had undergone significant wet scavenging (> 50% PM10) during transport. Modeled aerosol vertical distributions and optical properties below the aircraft are evaluated in the Arctic using airborne lidar measurements. Model results show that the pollution event transported aerosols into the Arctic (> 66.6° N) for a 4-day period. During this 4-day period, biomass burning emissions have the strongest influence on concentrations between 2.5 and 3 km altitudes, while European anthropogenic emissions influence aerosols at both lower (~ 1.5 km) and higher altitudes (~ 4.5 km). As a proportion of PM2.5, modeled black carbon and SO4= concentrations are more enhanced near the surface in anthropogenic plumes. The European plumes sampled during the POLARCAT-France campaign were transported over the region of springtime snow cover in northern Scandinavia, where they had a significant local atmospheric warming effect. We find that, during this transport event, the average modeled top-of-atmosphere (TOA) shortwave direct and semi-direct radiative effect (DSRE) north of 60° N over snow and ice-covered surfaces reaches +0.58 W m−2, peaking at +3.3 W m−2 at noon over Scandinavia and Finland.

Using observations from aircraft, surface stations and a satellite instrument, we comprehensively evaluate multi-model simulations of carbon monoxide (CO) and ozone (O3) in the Arctic and over lower latitude emission regions, as part of the POLARCAT Model Inter-comparison Project (POLMIP). Evaluation of 11- atmospheric models with chemistry shows that they generally underestimate CO throughout the Arctic troposphere, with the largest biases found during winter and spring. Negative CO biases are also found throughout the Northern Hemisphere, with multi-model mean gross errors (9–12%) suggesting models perform similarly over Asia, North America and Europe. A multi-model annual mean tropospheric OH (10.8 ± 0.6 × 105 molec cm−3) is found to be slightly higher than previous estimates of OH constrained by methyl chloroform, suggesting negative CO biases in models may be improved through better constraints on OH. Models that have lower Arctic OH do not always show a substantial improvement in their negative CO biases, suggesting that Arctic OH is not the dominant factor controlling the Arctic CO burden in these models. In addition to these general biases, models do not capture the magnitude of CO enhancements observed in the Arctic free troposphere in summer, suggesting model errors in the simulation of plumes that are transported from anthropogenic and biomass burning sources at lower latitudes. O3 in the Arctic is also generally underestimated, particularly at the surface and in the upper troposphere. Summer O3 comparisons over lower latitudes show several models overestimate upper tropospheric concentrations. Simulated CO, O3 and OH all demonstrate a substantial degree of inter-model variability. Idealised CO-like tracers are used to quantitatively compare the impact of inter-model differences in transport and OH on CO in the Arctic troposphere. The tracers show that model differences in transport from Europe in winter and from Asia throughout the year are important sources of model variability at Barrow. Unlike transport, inter-model variability in OH similarly affects all regional tracers at Barrow. Comparisons of fixed-lifetime and OH-loss idealised CO-like tracers throughout the Arctic troposphere show that OH differences are a much larger source of inter-model variability than transport differences. Model OH concentrations are correlated with H2O concentrations, suggesting water vapour concentrations are linked to differences in simulated concentrations of CO and OH at high latitudes in these simulations. Despite inter-model differences in transport and OH, the relative contributions from the different source regions (North America, Europe and Asia) and different source types (anthropogenic and biomass burning) are comparable across the models. Fire emissions from the boreal regions in 2008 contribute 33, 43 and 19% to the total Arctic CO-like tracer in spring, summer and autumn, respectively, highlighting the importance of boreal fire emissions in controlling pollutant burdens in the Arctic.

Emissions from oil/gas extraction activities in the Arctic are already important in certain regions and may increase as global warming opens up new opportunities for industrial development. Emissions from oil/gas extraction are sources of air pollutants, but large uncertainties exist with regard to their amounts and composition. In this study, we focus on detailed investigation of emissions from oil/gas extraction in the Norwegian Sea combining measurements from the EU ACCESS aircraft campaign in July 2012 and regional chemical transport modeling. The goal is to (1) evaluate emissions from petroleum extraction activities and (2) investigate their impact on atmospheric composition over the Norwegian Sea. Numerical simulations include emissions for permanently operating offshore facilities from two datasets: the TNO-MACC inventory and emissions reported by Norwegian Environment Agency (NEA). It was necessary to additionally estimate primary aerosol emissions using reported emission factors since these emissions are not included in the inventories for our sites. Model runs with the TNO-MACC emissions are unable to reproduce observations close to the facilities. Runs using the NEA emissions more closely reproduce the observations although emissions from mobile facilities are missing from this inventory. Measured plumes suggest they are a significant source of pollutants, in particular NOx and aerosols. Sensitivities to NOx and NMVOC emissions show that, close to the platforms, O3 is sensitive to NOx emissions and is much less sensitive to NMVOC emissions. O3 destruction, via reaction with NO, dominates very close to the platforms. Far from the platforms, oil/gas facility emissions result in an average daytime O3 enhancement of +2% at the surface. Larger enhancements are predicted at noon ranging from +7% at the surface to +15% at 600 m. Black carbon is the aerosol species most strongly influenced by petroleum extraction emissions. The results highlight significant uncertainties in emissions related to petroleum extraction emissions in the Arctic.

Over the Mediterranean region, elevated tropospheric ozone (O3) values are recorded, especially in summer. We use the thermal Infrared Atmospheric Sounding Interferometer (IASI) and the Weather Research and Forecasting Model with Chemistry (WRF-Chem) to understand and interpret the factors and emission sources responsible for the high O3 concentrations observed in the Mediterranean troposphere. Six years (2008–2013) of IASI data have been analyzed and results show consistent maxima during summer, with an increase of up to 22% in the [0–8] km O3 column in the eastern part of the basin compared to the middle of the basin. We focus on summer 2010 to investigate the processes that contribute to these summer maxima. Using two modeled O3 tracers (inflow to the model domain and local anthropogenic emissions), we show that, between the surface and 2 km, O3 is mostly formed from anthropogenic emissions, while above 4 km it is mostly transported from outside the domain or from stratospheric origins. Evidence of stratosphere-to-troposphere exchange (STE) events in the eastern part of the basin is shown, and corresponds to a low water vapor mixing ratio and high potential vorticity.

Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air–ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed.

We use observations of the absorption properties of black carbon and non-black carbon impurities in near-surface snow collected near the research stations at South Pole and Dome C, Antarctica, and Summit, Greenland, combined with a snowpack actinic flux parameterization to estimate the vertical profile and e-folding depth of ultraviolet/near-visible (UV/near-vis) actinic flux in the snowpack at each location. We have developed a simple and broadly applicable parameterization to calculate depth and wavelength dependent snowpack actinic flux that can be easily integrated into large-scale (e.g., 3-D) models of the atmosphere. The calculated e-folding depths of actinic flux at 305 nm, the peak wavelength of nitrate photolysis in the snowpack, are 8–12 cm near the stations and 15–31 cm away (>11 km) from the stations. We find that the e-folding depth is strongly dependent on impurity content and wavelength in the UV/near-vis region, which explains the relatively shallow e-folding depths near stations where local activities lead to higher snow impurity levels. We calculate the lifetime of NOx in the snowpack interstitial air produced by photolysis of snowpack nitrate against wind pumping (τwind pumping) from the snowpack, and compare this to the calculated lifetime of NOx against chemical conversion to HNO3 (τchemical) to determine whether the NOx produced at a given depth can escape from the snowpack to the overlying atmosphere. Comparison of τwind pumping and τchemical suggests efficient escape of photoproduced NOx in the snowpack to the overlying atmosphere throughout most of the photochemically active zone. Calculated vertical actinic flux profiles and observed snowpack nitrate concentrations are used to estimate the potential flux of NOx from the snowpack. Calculated NOx fluxes of 4.4 × 108–3.8 × 109 molecules cm−2 s−1 in remote polar locations and 3.2–8.2 × 108 molecules cm−2 s−1 near polar stations for January at Dome C and South Pole and June at Summit suggest that NOx flux measurements near stations may be underestimating the amount of NOx emitted from the clean polar snowpack.

Ozone pollution transported to the Arctic is a significant concern because of the rapid, enhanced warming in high northern latitudes, which is caused, in part, by short-lived climate forcers, such as ozone. Long-range transport of pollution contributes to background and episodic ozone levels in the Arctic. However, the extent to which plumes are photochemically active during transport, particularly during the summer, is still uncertain. In this study, regional chemical transport model simulations are used to examine photochemical production of ozone in air masses originating from boreal fire and anthropogenic emissions over North America and during their transport toward the Arctic during early July 2008. Model results are evaluated using POLARCAT aircraft data collected over boreal fire source regions in Canada (ARCTAS-B) and several days downwind over Greenland (POLARCAT-France and POLARCAT-GRACE). Model results are generally in good agreement with the observations, except for certain trace gas species over boreal fire regions, in some cases indicating that the fire emissions are too low. Anthropogenic and biomass burning pollution (BB) from North America was rapidly uplifted during transport east and north to Greenland where pollution plumes were observed in the mid- and upper troposphere during POLARCAT. A model sensitivity study shows that CO levels are in better agreement with POLARCAT measurements (fresh and aged fire plumes) upon doubling CO emissions from fires. Analysis of model results, using ΔO3/ΔCO enhancement ratios, shows that pollution plumes formed ozone during transport towards the Arctic. Fresh anthropogenic plumes have average ΔO3/ΔCO enhancement ratios of 0.63 increasing to 0.92 for aged anthropogenic plumes, indicating additional ozone production during aging. Fresh fire plumes are only slightly enhanced in ozone (ΔO3/ΔCO=0.08), but form ozone downwind with ΔO3/ΔCO of 0.49 for aged BB plumes (model-based run). We estimate that aged anthropogenic and BB pollution together made an important contribution to ozone levels with an average contribution for latitudes >55° N of up to 6.5 ppbv (18%) from anthropogenic pollution and 3 ppbv (5.2%) from fire pollution in the model domain in summer 2008.

From 10 May through 17 June 2007 and 6 June through 9 July 2008 intensive sampling campaigns at Summit, Greenland confirmed that active bromine chemistry is occurring in and above the snow pack at the highest part of the Greenland ice sheet (72°36´ N, 38°25´ W and 3.2 km above sea level). Direct measurements found BrO and soluble gas phase Br− mixing ratios in the low pptv range on many days (maxima < 10 pptv). Conversion of up to 200 pg m−3 of gaseous elemental mercury (GEM) to reactive gaseous mercury (RGM) and enhanced OH relative to HO2 plus RO2 confirm that active bromine chemistry is impacting chemical cycles even at such low abundances of reactive bromine species. However, it does not appear that Bry chemistry can fully account for observed perturbations to HOx partitioning, suggesting unknown additional chemical processes may be important in this unique environment, or that our understanding of coupled NOx-HOx-Bry chemistry above sunlit polar snow is incomplete. Rapid transport from the north Atlantic marine boundary layer occasionally caused enhanced BrO at Summit (just two such events observed during the 12 weeks of sampling over the two seasons). In general observed reactive bromine was linked to activation of bromide (Br−) in, and release of reactive bromine from, the snowpack. A coupled snow-atmosphere model simulated observed NO and BrO at Summit during a three day interval when winds were weak. The source of Br− in surface and near surface snow at Summit is not entirely clear, but concentrations were observed to increase when stronger vertical mixing brought free tropospheric air to the surface. Reactive Bry mixing ratios above the snow often increased in the day or two following increases in snow concentration, but this response was not consistent. On seasonal time scales concentrations of Br− in snow and reactive bromine in the air were directly related.

The role of ice in the formation of chemically active halogens in the environment requires a full understanding because of its role in atmospheric chemistry, including controlling the regional atmospheric oxidizing capacity in specific situations. In particular, ice and snow are important for facilitating multiphase oxidative chemistry and as media upon which marine algae live. This paper reviews the nature of environmental ice substrates that participate in halogen chemistry, describes the reactions that occur on such substrates, presents the field evidence for ice-mediated halogen activation, summarizes our best understanding of ice-halogen activation mechanisms, and describes the current state of modeling these processes at different scales. Given the rapid pace of developments in the field, this paper largely addresses advances made in the past five years, with emphasis given to the polar boundary layer. The integrative nature of this field is highlighted in the presentation of work from the molecular to the regional scale, with a focus on understanding fundamental processes. This is essential for developing realistic parameterizations and descriptions of these processes for inclusion in larger scale models that are used to determine their regional and global impacts.

The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. While it is acknowledged that the chemistry occurring at ice surfaces may consist of a true quasi-liquid layer and/or a concentrated brine layer, lack of additional knowledge requires that this chemistry be modeled as primarily aqueous chemistry occurring in a liquid-like layer (LLL) on snow grains. The model has been recently compared with BrO and NO data taken on 10 June–13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the mid-day OH concentrations. Bromine chemistry increases the OH concentration by 10–18% (10% at noon LT), while snow sourced NOx increases OH concentrations by 20–50% (27% at noon LT). We show for the first time, using a coupled one-dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown \chem{HONO} source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000, which had lower levels than other years. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss.

Reactive halogens, and in particular bromine oxide (BrO), have frequently been observed in regions with large halide reservoirs, for example during bromine catalyzed coastal polar ozone depletion events. Much less is known about the presence and impact of reactive halogens in areas without obvious halide reservoirs, such as the polar ice sheets or continental snow. We report the first LP-DOAS measurements of BrO at Summit research station in the center of the Greenland ice sheet at an altitude of 3200 m. BrO mixing ratios in May 2007 and June 2008 were typically between 1–3 pmol mol−1, with maxima of up to 5 pmol mol−1. These measurements unequivocally show that halogen chemistry is occurring in the remote Arctic, far from known bromine reservoirs, such as the ocean. During periods when FLEXPART retroplumes show that airmasses resided on the Greenland ice sheet for 3 or more days, BrO exhibits a clear diurnal variation, with peak mixing ratios of up to 3 pmol mol−1 in the morning and at night. The diurnal cycle of BrO can be explained by a changing boundary layer height combined with photochemical formation of reactive bromine driven by solar radiation at the snow surface. The shallow stable boundary layer in the morning and night leads to an accumulation of BrO at the surface, leading to elevated BrO despite the expected smaller release from the snowpack during these times of low solar radiation. During the day when photolytic formation of reactive bromine is expected to be highest, efficient mixing into a deeper neutral boundary layer leads to lower BrO mixing ratios than during mornings and nights. The extended period of contact with the Greenland snowpack combined with the diurnal profile of BrO, modulated by boundary layer height, suggests that photochemistry in the snow is a significant source of BrO measured at Summit during the 2008 experiment. In addition, a rapid transport event on 4 July 2008, during which marine air from the Greenland east coast was rapidly transported to Summit, led to enhanced mixing ratios of BrO and a number of marine tracers. However, rapid transport of marine air from the Greenland east coast is rare and most likely not the main source of bromide in surface snow at Summit. The observed levels of BrO are predicted to influence NOx chemistry as well as impact HOx partitioning. However, impact of local snow photochemistry on HOx is smaller than previously suggested for Summit.

The Greenland Summit Halogen-HOx (GSHOX) Campaign was performed in spring 2007 and summer 2008 to investigate the impact of halogens on HOx (= OH + HO2) cycling above the Greenland Ice Sheet. Chemical species including hydroxyl and peroxy radicals (OH and HO2 + RO2), ozone (O3), nitrogen oxide (NO), nitric acid (HNO3), nitrous acid (HONO), reactive gaseous mercury (RGM), and bromine oxide (BrO) were measured during the campaign. The median midday values of HO2 + RO2 and OH concentrations observed by chemical ionization mass spectrometry (CIMS) were 2.7 × 108 molec cm−3 and 3.0 × 106 molec cm−3 in spring 2007, and 4.2 × 108 molec cm−3 and 4.1 × 106 molec cm−3 in summer 2008. A basic photochemical 0-D box model highly constrained by observations of H2O, O3, CO, CH4, NO, and J values predicted HO2 + RO2 (R = 0.90, slope = 0.87 in 2007; R = 0.79, slope = 0.96 in 2008) reasonably well and under predicted OH (R = 0.83, slope = 0.72 in 2007; R = 0.76, slope = 0.54 in 2008). Constraining the model to HONO observations did not significantly improve the ratio of OH to HO2 + RO2 and the correlation between predictions and observations. Including bromine chemistry in the model constrained by observations of BrO improved the correlation between observed and predicted HO2 + RO2 and OH, and brought the average hourly OH and HO2 + RO2 predictions closer to the observations. These model comparisons confirmed our understanding of the dominant HOx sources and sinks in this environment and indicated that BrO impacted the OH levels at Summit. Although, significant discrepancies between observed and predicted OH could not be explained by the measured BrO. Finally, observations of enhanced RGM were found to be coincident with under prediction of OH.

Sun-lit snow is increasingly recognized as a chemical reactor that plays an active role in uptake, transformation, and release of atmospheric trace gases. Snow is known to influence boundary layer air on a local scale, and given the large global surface coverage of snow may also be significant on regional and global scales. We present a new detailed one-dimensional snow chemistry module that has been coupled to the 1-D atmospheric boundary layer model MISTRA. The new 1-D snow module, which is dynamically coupled to the overlaying atmospheric model, includes heat transport in the snowpack, molecular diffusion, and wind pumping of gases in the interstitial air. The model includes gas phase chemical reactions both in the interstitial air and the atmosphere. Heterogeneous and multiphase chemistry on atmospheric aerosol is considered explicitly. The chemical interaction of interstitial air with snow grains is simulated assuming chemistry in a liquid-like layer (LLL) on the grain surface. The coupled model, referred to as MISTRA-SNOW, was used to investigate snow as the source of nitrogen oxides (NOx) and gas phase reactive bromine in the atmospheric boundary layer in the remote snow covered Arctic (over the Greenland ice sheet) as well as to investigate the link between halogen cycling and ozone depletion that has been observed in interstitial air. The model is validated using data taken 10 June–13 June, 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). The model predicts that reactions involving bromide and nitrate impurities in the surface snow can sustain atmospheric NO and BrO mixing ratios measured at Summit, Greenland during this period.