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The marginal sea ice zone has been identified as a source of different climate-active gases to the atmosphere due to its unique biogeochemistry. However, it remains highly undersampled, and the impact of summertime changes in sea ice concentration on the distributions of these gases is poorly understood. To address this, we present measurements of dissolved methanol, acetone, acetaldehyde, dimethyl sulfide, and isoprene in the sea ice zone of the Canadian Arctic from the surface down to 60 m. The measurements were made using a segmented flow coil equilibrator coupled to a proton-transfer-reaction mass spectrometer. These gases varied in concentrations with depth, with the highest concentrations generally observed near the surface. Underway (3–4 m) measurements showed higher concentrations in partial sea ice cover compared to ice-free waters for most compounds. The large number of depth profiles at different sea ice concentrations enables the proposition of the likely dominant production processes of these compounds in this area. Methanol concentrations appear to be controlled by specific biological consumption processes. Acetone and acetaldehyde concentrations are influenced by the penetration depth of light and stratification, implying dominant photochemical sources in this area. Dimethyl sulfide and isoprene both display higher surface concentrations in partial sea ice cover compared to ice-free waters due to ice edge blooms. Differences in underway concentrations based on sampling region suggest that water masses moving away from the ice edge influences dissolved gas concentrations. Dimethyl sulfide concentrations sometimes display a subsurface maximum in ice -free conditions, while isoprene more reliably displays a subsurface maximum. Surface gas concentrations were used to estimate their air–sea fluxes. Despite obvious in situ production, we estimate that the sea ice zone is absorbing methanol and acetone from the atmosphere. In contrast, dimethyl sulfide and isoprene are consistently emitted from the ocean, with marked episodes of high emissions during ice-free conditions, suggesting that these gases are produced in ice-covered areas and emitted once the ice has melted. Our measurements show that the seawater concentrations and air–sea fluxes of these gases are clearly impacted by sea ice concentration. These novel measurements and insights will allow us to better constrain the cycling of these gases in the polar regions and their effect on the oxidative capacity and aerosol budget in the Arctic atmosphere. [ABSTRACT FROM AUTHOR]

The marginal sea ice zone has been identified as a source of different climate active gases to the atmosphere due to its unique biogeochemistry. However, it remains highly undersampled and the impact of changes in sea ice concentration on the distributions of these gases is poorly understood. To address this, we present measurements of dissolved methanol, acetone, acetaldehyde, dimethyl sulfide and isoprene in the sea ice zone of the Canadian Arctic from the surface down to 60 m. The measurements were made using a Segmented Flow Coil Equilibrator coupled to a Proton Transfer Reaction Mass Spectrometer. These gases varied in concentrations with depth, with the highest concentrations generally observed near the surface. Underway (3-4 m) measurements showed broadly higher concentrations in partial sea ice cover compared to ice-free waters. The large number of depth profiles at different sea ice coverages enables proposition of the likely dominant production processes of these compounds in this area. Methanol concentrations appear to be controlled by specific biological consumption processes. Acetone and acetaldehyde concentrations are influenced by the penetration depth of light and the mixed layer depth, implying dominant photochemical sources in this area. Dimethyl sulfide and isoprene both display higher surface concentrations in partial sea ice coverage compared to ice-free waters due to ice edge blooms. Dimethyl sulfide concentrations sometimes display a subsurface maximum in ice -free conditions, while isoprene displays more reliably a subsurface maximum. Surface gas concentrations were used to estimate their air -- sea fluxes. Despite obvious in situ production, we estimate that the sea ice zone is absorbing methanol and acetone from the atmosphere. In contrast, DMS and isoprene are consistently emitted from the ocean, with marked episodes of high emissions during ice-free conditions, suggesting that these gases are produced in ice-covered areas and emitted once the ice has melted. Our measurements show that the seawater concentrations and air-sea fluxes of these gases are clearly impacted by sea ice concentration. These novel measurements and insights will allow us to better constrain the cycling of these gases in the polar regions and their effect on the oxidative capacity and aerosol budget in the Arctic atmosphere. [ABSTRACT FROM AUTHOR]

Dimethyl sulfide and volatile organic compounds (VOCs) are important for atmospheric chemistry. The emissions of biogenically derived organic gases, including dimethyl sulfide and especially isoprene, are not well constrained in the Southern Ocean. Due to a paucity of measurements, the role of the ocean in the atmospheric budgets of atmospheric methanol, acetone, and acetaldehyde is even more poorly known. In order to quantify the air–sea fluxes of these gases, we measured their seawater concentrations and air mixing ratios in the Atlantic sector of the Southern Ocean, along a ∼ 11 000 km long transect at approximately 60 ∘ S in February–April 2019. Concentrations, oceanic saturations, and estimated fluxes of five simultaneously sampled gases (dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde) are presented here. Campaign mean (±1σ) surface water concentrations of dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde were 2.60 (±3.94), 0.0133 (±0.0063), 67 (±35), 5.5 (±2.5), and 2.6 (±2.7) nmol dm -3 respectively. In this dataset, seawater isoprene and methanol concentrations correlated positively. Furthermore, seawater acetone, methanol, and isoprene concentrations were found to correlate negatively with the fugacity of carbon dioxide, possibly due to a common biological origin. Campaign mean (±1σ) air mixing ratios of dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde were 0.17 (±0.09), 0.053 (±0.034), 0.17 (±0.08), 0.081 (±0.031), and 0.049 (±0.040) ppbv. We observed diel changes in averaged acetaldehyde concentrations in seawater and ambient air (and to a lesser degree also for acetone and isoprene), which suggest light-driven production. Campaign mean (±1σ) fluxes of 4.3 (±7.4) µ mol m -2 d -1 DMS and 0.028 (±0.021) µ mol m -2 d -1 isoprene are determined where a positive flux indicates from the ocean to the atmosphere. Methanol was largely undersaturated in the surface ocean with a mean (±1σ) net flux of -2.4 (±4.7) µ mol m -2 d -1 , but it also had a few occasional episodes of outgassing. This section of the Southern Ocean was found to be a source and a sink for acetone and acetaldehyde this time of the year, depending on location, resulting in a mean net flux of -0.55 (±1.14) µ mol m -2 d -1 for acetone and -0.28 (±1.22) µ mol m -2 d -1 for acetaldehyde. The data collected here will be important for constraining the air–sea exchange, cycling, and atmospheric impact of these gases, especially over the Southern Ocean. [ABSTRACT FROM AUTHOR]

Abstract: Alkyl nitrates (C1–C5) were measured at two sites (near urban and rural) in southeast England during the Tropospheric Organic Chemistry Experiment (TORCH). Methyl nitrate was the dominant species during both campaigns accounting for on average about one third of the total measured alkyl nitrates. High mixing ratios (>50 pptv) and variability of methyl nitrate were observed at the near urban site (TORCH1) that were not seen at the rural site (TORCH2) and which could not be explained by local photochemical production or direct emissions. The diurnal variation of methyl nitrate during TORCH1 showed a morning maximum that would be consistent with nighttime chemistry followed by transport to the surface by boundary layer dynamics. Similarly, elevated morning mixing ratios were also observed during TORCH2 although the magnitudes were much smaller. As a result, methyl nitrate could represent a tracer for nighttime chemistry seen at the ground the following day. At both campaigns, the dominant source of short chain alkyl nitrates and carbonyl precursor radicals (≤C4) were from decomposition of larger compounds. The magnitude of the source increased with decreasing carbon number consistent with increasing total precursor abundance. Non-photochemical emissions of acetaldehyde and acetone could not be accounted for by automobile exhaust emissions alone and indicated that other direct sources are likely important in this environment. [Copyright &y& Elsevier]