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Reactive organic carbon (ROC) is diverse in its speciation, functionalization, and volatility, with varying implications for ozone production and secondary organic aerosol formation and growth. Chemical ionization mass spectrometry (CIMS) approaches can provide in situ ROC observations, and the CIMS reagent ion controls the detectable ROC species. To expand the range of detectable ROC, we describe a method for switching between the reagent ions NH4+ and H3O+ in a Vocus chemical ionization time-of-flight mass spectrometer (Vocus-CI-ToFMS). We describe optimization of ion–molecule reactor conditions for both reagent ions, at the same temperature, and compare the ability of NH4+ and H3O+ to detect a variety of volatile organic compounds (VOCs) and semi-volatile and intermediate-volatility organic compounds (SVOCs and IVOCs), including oxygenates and organic sulfur compounds. Sensitivities are comparable to other similar instruments (up to ∼5 counts /s /pptv), with detection limits on the order of 1–10 s of pptv (1 s integration time). We report a method for characterizing and filtering periods of hysteresis following each reagent ion switch and compare use of reagent ions, persistent ambient ions, and a deuterated internal standard for diagnosing this hysteresis. We deploy NH4+/H3O+ reagent ion switching in a rural pine forest in central Colorado, US, and use our ambient measurements to compare the capabilities of NH4+ and H3O+ in the same instrument, without interferences from variation in instrument and inlet designs. We find that H3O+ optimally detects reduced ROC species with high volatility, while NH4+ improves detection of functionalized ROC compounds, including organic nitrates and oxygenated SVOCs and IVOCs that are readily fragmented by H3O+. 

Polar oceans and sea ice cover 15% of the Earth’s ocean surface, and the environment is changing rapidly at both poles. Improving knowledge on the interactions between the atmospheric and oceanic realms in the polar regions, a Surface Ocean–Lower Atmosphere Study (SOLAS) project key focus, is essential to understanding the Earth system in the context of climate change. However, our ability to monitor the pace and magnitude of changes in the polar regions and evaluate their impacts for the rest of the globe is limited by both remoteness and sea-ice coverage. Sea ice not only supports biological activity and mediates gas and aerosol exchange but can also hinder some in-situ and remote sensing observations. While satellite remote sensing provides the baseline climate record for sea-ice properties and extent, these techniques cannot provide key variables within and below sea ice. Recent robotics, modeling, and in-situ measurement advances have opened new possibilities for understanding the ocean–sea ice–atmosphere system, but critical knowledge gaps remain. Seasonal and long-term observations are clearly lacking across all variables and phases. Observational and modeling efforts across the sea-ice, ocean, and atmospheric domains must be better linked to achieve a system-level understanding of polar ocean and sea-ice environments. As polar oceans are warming and sea ice is becoming thinner and more ephemeral than before, dramatic changes over a suite of physicochemical and biogeochemical processes are expected, if not already underway. These changes in sea-ice and ocean conditions will affect atmospheric processes by modifying the production of aerosols, aerosol precursors, reactive halogens and oxidants, and the exchange of greenhouse gases. Quantifying which processes will be enhanced or reduced by climate change calls for tailored monitoring programs for high-latitude ocean environments. Open questions in this coupled system will be best resolved by leveraging ongoing international and multidisciplinary programs, such as efforts led by SOLAS, to link research across the ocean–sea ice–atmosphere interface. 

Abstract. 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<15 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.