Abstract. The first multi-year contributions from organic functional groups to the Arctic submicron aerosol are documented using 126 weekly-integrated samples collected from April 2012 to October 2014 at the Alert Observatory (82.45 • N, 62.51 • W). Results from the particle transport model FLEXPART, linear regressions among the organic and inorganic components and positive matrix factorization (PMF) enable associations of organic aerosol components with source types and regions. Lower organic mass (OM) concentrations but higher ratios of OM to non-sea-salt sulfate mass concentrations (nss-SO = 4 ) accompany smaller particles during the summer (JJA). Conversely, higher OM but lower OM / nss-SO = 4 accompany larger particles during winter-spring. OM ranges from 7 to 460 ng m −3 , and the study average is 129 ng m −3 . The monthly maximum in OM occurs during May, 1 month after the peak in nss-SO = 4 and 2 months after that of elemental carbon (EC). Winter (DJF), spring (MAM), summer and fall (SON) values of OM / nss-SO = 4 are 26, 28, 107 and 39 %, respectively, and overall about 40 % of the weekly variability in the OM is associated with nss-SO = 4 . Respective study-averaged concentrations of alkane, alcohol, acid, amine and carbonyl groups are 57, 24, 23, 15 and 11 ng m −3 , representing 42, 22, 18, 14 and 5 % of the OM, respectively. Carbonyl groups, detected mostly during spring, may have a connection with snow chemistry. The seasonally highest O / C occurs during winter (0.85) and the lowest O / C is during spring (0.51); increases in O / C are largely due to increases in alcohol groups. During winter, more than 50 % of the alcohol groups are associated with primary marine emissions, consistent with Shaw et al. (2010) and Frossard et al. (2011). A secondary marine connection, rather than a primary source, is suggested for the highest and most persistent O / C observed during the coolest and cleanest summer (2013), when alcohol and acid groups made up 63 % of the OM. A secondary marine source may be a general feature of the summer OM, but higher contributions from alkane groups to OM during the warmer summers of 2012 (53 %) and 2014 (50 %) were likely due to increased contributions from combustion sources. Evidence for significant contributions from biomass burning (BB) was present in 4 % of the weeks. During the dark months (NDJF), 29, 28 and 14 % of the nss-SO = 4 , EC and OM were associated with transport times over the gas flaring region of northern Russia and other parts of Eurasia. During spring, those percentages dropped to 11 % for each of nss-SO = 4 and EC values, respectively, and there is no association of OM.

Abstract. 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).

Abstract. Absorption of sunlight by black carbon (BC) warms the atmosphere, which may be important for Arctic climate. The measurement of BC is complicated by the lack of a simple definition of BC and the absence of techniques that are uniquely sensitive to BC (e.g., Petzold et al., 2013). At the Global Atmosphere Watch baseline observatory in Alert, Nunavut (82.5 • N), BC mass is estimated in three ways, none of which fully represent BC: conversion of light absorption measured with an Aethalometer to give equivalent black carbon (EBC), thermal desorption of elemental carbon (EC) from weekly integrated filter samples to give EC, and measurement of incandescence from the refractory black carbon (rBC) component of individual particles using a single particle soot photometer (SP2). Based on measurements between March 2011 and December 2013, EBC and EC are 2.7 and 3.1 times higher than rBC, respectively. The EBC and EC measurements are influenced by factors other than just BC, and higher estimates of BC are expected from these techniques. Some bias in the rBC measurement may result from calibration uncertainties that are difficult to estimate here. Considering a number of factors, our best estimate of BC mass in Alert, which may be useful for evaluation of chemical transport models, is an average of the rBC and EC measurements with a range bounded by the rBC and EC combined with the respective measurement uncertainties. Winter-, spring-, summer-, and fall-averaged (± atmospheric variability) estimates of BC mass in Alert for this study period are 49 ± 28, 30 ± 26, 22 ± 13, and 29 ± 9 ng m −3 , respectively. Average coating thicknesses estimated from the SP2 are 25 to 40 % of the 160-180 nm diameter rBC core sizes. For particles of approximately 200-400 nm optical diameter, the fraction containing rBC cores is estimated to be between 10 and 16 %, but the possibility of smaller undetectable rBC cores in some of the particles cannot be excluded. Mass absorption coefficients (MACs) ± uncertainty at 550 nm wavelength, calculated from light absorption measurements divided by the best estimates of the BC mass concentrations, are 8.0 ± 4.0, 8.0 ± 4.0, 5.0 ± 2.5 and 9.0 ± 4.5 m 2 g −1 , for winter, spring, summer, and fall, respectively. Adjusted to better estimate absorption by BC only, the winter and spring values of MACs are 7.6 ± 3.8 and 7.7 ± 3.8 m 2 g −1 . There is evidence that the MAC values increase with coating thickness.

Abstract. The Optical Spectrograph and Infra-Red Imager System (OSIRIS) and the Atmospheric Chemistry Experiment (ACE) have been taking measurements from space since 2001 and 2003, respectively. This paper presents intercomparisons between ozone and NO 2 measured by the ACE and OSIRIS satellite instruments and by groundbased instruments at the Polar Environment Atmospheric Research Laboratory (PEARL), which is located at Eureka, Canada (80 • N, 86 • W) and is operated by the Canadian Network for the Detection of Atmospheric Change (CANDAC). The ground-based instruments included in this study are four zenith-sky differential optical absorption spectroscopy (DOAS) instruments, one Bruker Fourier transform infrared spectrometer (FTIR) and four Brewer spectrophotometers.Ozone total columns measured by the DOAS instruments were retrieved using new Network for the Detection of Atmospheric Composition Change (NDACC) guidelines and agree to within 3.2 %. The DOAS ozone columns agree with the Brewer spectrophotometers with mean relative differences that are smaller than 1.5 %. This suggests that for these instruments the new NDACC data guidelines were successful in producing a homogenous and accurate ozone dataset at 80 • N. Satellite 14-52 km ozone and 17-40 km NO 2 partial columns within 500 km of PEARL were calculated for ACE-FTS Version 2.2 (v2.2) plus updates, ACE- C. Adams et al.: Validation of ACE and OSIRISand Optimal Estimation v3.0 NO 2 data products. The new ACE-FTS v3.0 and the validated ACE-FTS v2.2 partial columns are nearly identical, with mean relative differences of 0.0 ± 0.2 % and −0.2 ± 0.1 % for v2.2 minus v3.0 ozone and NO 2 , respectively. Ozone columns were constructed from 14-52 km satellite and 0-14 km ozonesonde partial columns and compared with the ground-based total column measurements. The satellite-plus-sonde measurements agree with the ground-based ozone total columns with mean relative differences of 0.1-7.3 %. For NO 2 , partial columns from 17 km upward were scaled to noon using a photochemical model. Mean relative differences between OSIRIS, ACE-FTS and ground-based NO 2 measurements do not exceed 20 %. ACE-MAESTRO measures more NO 2 than the other instruments, with mean relative differences of 25-52 %. Seasonal variation in the differences between NO 2 partial columns is observed, suggesting that there are systematic errors in the measurements and/or the photochemical model corrections. For ozone spring-time measurements, additional coincidence criteria based on stratospheric temperature and the location of the polar vortex were found to improve agreement between some of the instruments. For ACE-FTS v2.2 minus Bruker FTIR, the 2007-2009 spring-time mean relative difference improved from −5.0 ± 0.4 % to −3.1 ± 0.8 % with the dynamical selection criteria. This was the largest improvement, likely because both instruments measure direct sunlight and therefore have well-characterized lines-of-sight compared with scattered sunlight measurements. For NO 2 , the addition of a ±1 • latitude co...

Abstract. We report on HCFC-22 data acquired by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) in the reduced spectral resolution nominal observation mode. The data cover the period from January 2005 to April 2012 and the altitude range from the upper troposphere (above cloud top altitude) to about 50 km. The profile retrieval was performed by constrained nonlinear least squares fitting of modelled spectra to the measured limb spectral radiances. The spectral ν4-band at 816.5 ± 13 cm−1 was used for the retrieval. A Tikhonov-type smoothing constraint was applied to stabilise the retrieval. In the lower stratosphere, we find a global volume mixing ratio of HCFC-22 of about 185 pptv in January 2005. The rate of linear growth in the lower latitudes lower stratosphere was about 6 to 7 pptv year−1 in the period 2005–2012. The profiles obtained were compared with ACE-FTS satellite data v3.5, as well as with MkIV balloon profiles and cryosampler balloon measurements. Between 13 and 22 km, average agreement within −3 to +5 pptv (MIPAS – ACE) with ACE-FTS v3.5 profiles is demonstrated. Agreement with MkIV solar occultation balloon-borne measurements is within 10–20 pptv below 30 km and worse above, while in situ cryosampler balloon measurements are systematically lower over their full altitude range by 15–50 pptv below 24 km and less than 10 pptv above 28 km. MIPAS HCFC-22 time series below 10 km altitude are shown to agree mostly well to corresponding time series of near-surface abundances from the NOAA/ESRL and AGAGE networks, although a more pronounced seasonal cycle is obvious in the satellite data. This is attributed to tropopause altitude fluctuations and subsidence of polar winter stratospheric air into the troposphere. A parametric model consisting of constant, linear, quasi-biennial oscillation (QBO) and several sine and cosine terms with different periods has been fitted to the temporal variation of stratospheric HCFC-22 for all 10°-latitude/1-to-2-km-altitude bins. The relative linear variation was always positive, with relative increases of 40–70 % decade−1 in the tropics and global lower stratosphere, and up to 120 % decade−1 in the upper stratosphere of the northern polar region and the southern extratropical hemisphere. Asian HCFC-22 emissions have become the major source of global upper tropospheric HCFC-22. In the upper troposphere, monsoon air, rich in HCFC-22, is instantaneously mixed into the tropics. In the middle stratosphere, between 20 and 30 km, the observed trend is inconsistent with the trend at the surface (corrected for the age of stratospheric air), hinting at circulation changes. There exists a stronger positive trend in HCFC-22 in the Southern Hemisphere and a more muted positive trend in the Northern Hemisphere, implying a potential change in the stratospheric circulation over the observation period.