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The flux of CO 2 between the atmosphere and the ocean is often estimated as the air–sea gas concentration difference multiplied by the gas transfer velocity ( K 660 ). The first order driver for K 660 over the ocean is wind through its influence on near surface hydrodynamics. However, field observations have shown substantial variability in the wind speed dependencies of K 660 . In this study we measured K 660 with the eddy covariance technique during a ~ 11,000 km long Southern Ocean transect. In parallel, we made a novel measurement of the gas transfer efficiency (GTE) based on partial equilibration of CO 2 using a Segmented Flow Coil Equilibrator system. GTE varied by 20% during the transect, was distinct in different water masses, and related to K 660 . At a moderate wind speed of 7 m s −1 , K 660 associated with high GTE exceeded K 660 with low GTE by 30% in the mean. The sensitivity of K 660 towards GTE was stronger at lower wind speeds and weaker at higher wind speeds. Naturally-occurring organics in seawater, some of which are surface active, may be the cause of the variability in GTE and in K 660 . Neglecting these variations could result in biases in the computed air–sea CO 2 fluxes.

Biological activity in the surface ocean leads to emissions of methanethiol (MeSH) and dimethyl sulfide (DMS). Measurements of MeSH in the marine atmosphere are sparse and the impact of NOx pollution on MeSH oxidation remains unexplored. We present measurements of MeSH and DMS at a coastal site with NOx up to 24.3 ppb in the United Kingdom during May and June. Winds coming from the seaward (northerly) direction showed a median (25th quantiles) MeSH mixing ratio of 15.7 (7.9–26.9)  ppt. The measurements reveal significantly lower MeSH during daytime. Atmospheric box model calculations suggest that ∼25% of the MeSH oxidation is initiated by NO3 at this site and that NOx pollution can reduce the SO2 yield from MeSH. This work is further evidence for the prevalence of MeSH and illustrates the impact of NOx pollution on MeSH oxidation with associated implications for its role in aerosol‐cloud processes, and climate. Plain Language Summary The oceans emit substantial amounts of volatile, gaseous sulfur in the form of methanethiol and DMS. Methanethiol measurements in marine air are very sparse, partly because it is hard to measure. Methanethiol is of interest, because it very efficiently reacts in the atmosphere to form SO2 at a close to 100% yield. SO2 is a particle forming sulfur gas, cooling the climate. We measured methanethiol in air on the UK coast and found it to be present at 10–30 ppt, a tiny fraction of the molecules in air. We find higher mixing ratios when the winds are from the sea, likely because the oceans are emitting this compound. We also find higher mixing ratios at night, probably due to removal processes initiated by sunlight and physical processes in the atmosphere. Using a computer model, we calculate that nitrogen oxides from shipping exhausts and terrestrial combustion sources can react with methanethiol at night. They have the potential to decrease the efficiency of SO2 production from methanethiol down to a yield of less than 50%. This case study gives a better appreciation of methanethiol's climatic impact and how this might be different in a polluted marine atmosphere. Key Points Measurements confirm that methanethiol is prevalent at typically 5–25 ppt at a coastal site in UK Mixing ratios are higher when winds are from the ocean and at night, likely due to ocean emissions and daytime OH oxidation Box modeling highlights NO3 as an important oxidant for MeSH and that NOx pollution has the potential to decrease the SO2 yield from MeSH

A range of volatile organic compounds (VOCs) have been found to be released during zooplankton grazing on microalgae cultivated for commercial purposes. However, production of grazing-derived VOCs from environmentally relevant species and their potential contribution to oceanic emissions to the atmosphere remains largely unexplored. Here, we aimed to qualitatively explore the suite of VOCs produced due to grazing using laboratory cultures of the marine microalga Isochrysis galbana and the herbivorous heterotrophic dinoflagellate Oxyrrhis marina with and without antibiotic treatment. The VOCs were measured using a Vocus proton-transfer-reaction time-of-flight mass spectrometer, coupled to a segmented flow coil equilibrator. We found alternative increases of dimethyl sulfide by up to 0.2 nmol dm−3 and methanethiol by up to 10 pmol dm−3 depending on the presence or absence of bacteria regulated by antibiotic treatment. Additionally, toluene and xylene increased by about 30 pmol dm−3 and 10 pmol dm−3, respectively during grazing only, supporting a biological source for these compounds. Overall, our results highlight that VOCs beyond dimethyl sulfide are released due to grazing, and prompt further quantification of this source in budgets and process-based understanding of VOC cycling in the surface ocean.

Volatile organic compounds (VOCs) are ubiquitous in the atmosphere and are important for atmospheric chemistry. Large uncertainties remain in the role of the ocean in the atmospheric VOC budget because of poorly constrained marine sources and sinks. There are very few direct measurements of air–sea VOC fluxes near the coast, where natural marine emissions could influence coastal air quality (i.e. ozone, aerosols) and terrestrial gaseous emissions could be taken up by the coastal seas. To address this, we present air–sea flux measurements of acetone, acetaldehyde and dimethylsulfide (DMS) at the coastal Penlee Point Atmospheric Observatory (PPAO) in the south-west UK during the spring (April–May 2018). Fluxes of these gases were measured simultaneously by eddy covariance (EC) using a proton-transfer-reaction quadrupole mass spectrometer. Comparisons are made between two wind sectors representative of different air–water exchange regimes: the open-water sector facing the North Atlantic Ocean and the terrestrially influenced Plymouth Sound fed by two estuaries. Mean EC (± 1 standard error) fluxes of acetone, acetaldehyde and DMS from the open-water wind sector were −8.0 ± 0.8, −1.6 ± 1.4 and 4.7 ± 0.6 µmol m−2 d−1 respectively (“−” sign indicates net air-to-sea deposition). These measurements are generally comparable (same order of magnitude) to previous measurements in the eastern North Atlantic Ocean at the same latitude. In comparison, the Plymouth Sound wind sector showed respective fluxes of −12.9 ± 1.4, −4.5 ± 1.7 and 1.8 ± 0.8 µmol m−2 d−1. The greater deposition fluxes of acetone and acetaldehyde within the Plymouth Sound were likely to a large degree driven by higher atmospheric concentrations from the terrestrial wind sector. The reduced DMS emission from the Plymouth Sound was caused by a combination of lower wind speed and likely lower dissolved concentrations as a result of the estuarine influence (i.e. dilution). In addition, we measured the near-surface seawater concentrations of acetone, acetaldehyde, DMS and isoprene from a marine station 6 km offshore. Comparisons are made between EC fluxes from the open-water and bulk air–sea VOC fluxes calculated using air and water concentrations with a two-layer (TL) model of gas transfer. The calculated TL fluxes agree with the EC measurements with respect to the directions and magnitudes of fluxes, implying that any recently proposed surface emissions of acetone and acetaldehyde would be within the propagated uncertainty of 2.6 µmol m−2 d−1. The computed transfer velocities of DMS, acetone and acetaldehyde from the EC fluxes and air and water concentrations are largely consistent with previous transfer velocity estimates from the open ocean. This suggests that wind, rather than bottom-driven turbulence and current velocity, is the main driver for gas exchange within the open-water sector at PPAO (depth of ∼ 20 m).

Volatile organic compounds (VOCs) are a group of molecules that influence aspects of atmospheric chemistry such as oxidation chemistry and particle formation. Most VOCs are produced from a variety of anthropogenic and natural sources; with emissions from the oceans least well known/ quantified. In this thesis I focus on methanol, acetone, acetaldehyde, DMS and isoprene. Uncertainty persists as to the factors influencing their variability in seawater concentrations. The polar oceans are particularly undersampled regions with few to no measurements of these compounds, which is partially due to a lack of suitable instrumentation. To increase available instrumentation, this thesis describes the development of a Segmented Flow Coil Equilibrator coupled to a commercially available Proton Transfer Reaction-Mass Spectrometer for measurements of VOCs in seawater. Its main advantage lies in its ability to measure underway and discrete samples. The method is used to make depth profile and underway measurements in the Canadian Arctic Archipelago during sea ice melt season. Highest VOC concentrations are generally observed at the surface, apart from DMS and isoprene which sometimes display a subsurface maximum. Generally, highest surface concentrations of VOCs are observed in partial ice cover. Concentrations of acetone and acetaldehyde were about 30 - 50 % higher in partial ice cover compared to ice-free waters. This thesis also presents ambient air, underway and depth profile measurements from a transect in the subpolar Southern Ocean, used to calculate surface saturations and air - sea fluxes. Correlations with other biogeochemical data allowed me to elucidate factors controlling seawater concentrations of these VOCs. This dataset contains the first evidence of a statistically significant, but small diel change (on the order of 8 - 26 %) in seawater isoprene, acetone and acetaldehyde concentrations in the open ocean. The measurements presented in this thesis will be useful to constrain ocean source/sink strength. The analysis points towards factors controlling the global variability of these compounds in the ocean.

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) µmol m−2 d−1 DMS and 0.028 (±0.021) µmol 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) µmol 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) µmol m−2 d−1 for acetone and −0.28 (±1.22) µmol 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.

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.

Alkylamines, volatile organic nitrogen compounds with low molecular weight, are present in the surface ocean and participate in the marine biogeochemical nitrogen cycle, atmospheric chemistry and cloud formation. Alkylamines have been detected in polar regions, suggesting that these areas constitute emission hotspots of these compounds. However, knowledge of the sea surface distribution patterns and factors modulating alkylamines remain limited due to their high reactivity and low concentrations, which hamper accurate measurements. We investigated the presence and distribution of alkylamines in seawaters around the Antarctic Peninsula and the northern Weddell Sea during the late austral summer and explored their potential links to marine microbiota. Alkylamines were ubiquitous in all analysed samples, accounting for ∼ 2 % of the dissolved and particulate organic nitrogen pool. The only particulate form found was trimethylamine (TMA), detected for the first time in Antarctic waters at concentrations of 9.7 ± 4.6 nM. We efficiently measured dissolved trimethylamine (TMA, 20.9 ± 15.2 nM), dimethylamine (DMA, 32.3 ± 32.7 nM) and diethylamine (DEA, 7.2 ± 1.7 nM) across the surveyed area, while dissolved monomethylamine (MMA, 12.7 ± 0.1 nM) remained below the detection limit in most samples. Variations in alkylamine concentrations did not align with the overall phytoplankton biomass but with specific biological components. TMA was predominantly associated with, and released from, nanophytoplankton. DMA was likely produced by the degradation of TMA or trimethylamine oxide by nanophytoplankton cells or associated heterotrophic bacteria. The sources of DEA remain unclear but were suggestive of a distinct biogeochemical pathway from those of TMA and DMA. MMA is thought to primarily originate from bacterial degradation of nitrogen-based osmolytes or amino acids, but detection in too few samples precluded any robust association with microbiota. This study reveals that volatile alkylamines are widespread in Antarctic surface waters, where they are primarily sourced from nanophytoplankton cells and associated heterotrophic bacteria and protists.

We present a technique that utilises a segmented flow coil equilibrator coupled to a proton-transfer-reaction mass spectrometer to measure a broad range of dissolved volatile organic compounds. Thanks to its relatively large surface area for gas exchange, small internal volume, and smooth headspace–water separation, the equilibrator is highly efficient for gas exchange and has a fast response time (under 1 min). The system allows for both continuous and discrete measurements of volatile organic compounds in seawater due to its low sample water flow (100 cm3 min−1) and the ease of changing sample intake. The equilibrator setup is both relatively inexpensive and compact. Hence, it can be easily reproduced and installed on a variety of oceanic platforms, particularly where space is limited. The internal area of the equilibrator is smooth and unreactive. Thus, the segmented flow coil equilibrator is expected to be less sensitive to biofouling and easier to clean than membrane-based equilibration systems. The equilibrator described here fully equilibrates for gases that are similarly soluble or more soluble than toluene and can easily be modified to fully equilibrate for even less soluble gases. The method has been successfully deployed in the Canadian Arctic. Some example data from underway surface water and Niskin bottle measurements in the sea ice zone are presented to illustrate the efficacy of this measurement system.

Natural processes in the polar oceans lead to emission of a variety of reactive gases contributing to atmospheric chemistry and aerosol formation. The identity and air–sea fluxes of most of these gases are poorly characterized, bringing uncertainty to the assessment of pre-industrial aerosol sources. Here we present seawater and atmospheric measurements of benzene and toluene in the open Southern Ocean and the Arctic marginal ice zone. Our data suggest a marine biogenic source for these two compounds, which have typically been associated with anthropogenic pollution. Calculated average emission fluxes were 0.024 and 0.037 μmol m-2 d-1 for benzene and toluene, respectively. Including the observed emissions in a chemistry–climate model increased secondary organic aerosol mass concentrations only by 0.1–1.2 % over the Arctic but by 7.7–77.3 % over the Southern Ocean far from continental sources. Climate models must consider the hitherto overlooked emissions of biogenic benzene and toluene from pristine oceanic regions.