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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 flow (flux) of climate-critical gases, such as carbon dioxide (CO2), between the ocean and the atmosphere is a fundamental component of our climate and an important driver of the biogeochemical systems within the oceans. Therefore, the accurate calculation of these air–sea gas fluxes is critical if we are to monitor the oceans and assess the impact that these gases are having on Earth's climate and ecosystems. FluxEngine is an open-source software toolbox that allows users to easily perform calculations of air–sea gas fluxes from model, in situ, and Earth observation data. The original development and verification of the toolbox was described in a previous publication. The toolbox has now been considerably updated to allow for its use as a Python library, to enable simplified installation, to ensure verification of its installation, to enable the handling of multiple sparingly soluble gases, and to enable the greatly expanded functionality for supporting in situ dataset analyses. This new functionality for supporting in situ analyses includes user-defined grids, time periods and projections, the ability to reanalyse in situ CO2 data to a common temperature dataset, and the ability to easily calculate gas fluxes using in situ data from drifting buoys, fixed moorings, and research cruises. Here we describe these new capabilities and demonstrate their application through illustrative case studies. The first case study demonstrates the workflow for accurately calculating CO2 fluxes using in situ data from four research cruises from the Surface Ocean CO2 ATlas (SOCAT) database. The second case study calculates air–sea CO2 fluxes using in situ data from a fixed monitoring station in the Baltic Sea. The third case study focuses on nitrous oxide (N2O) and, through a user-defined gas transfer parameterisation, identifies that biological surfactants in the North Atlantic could suppress individual N2O sea–air gas fluxes by up to 13 %. The fourth and final case study illustrates how a dissipation-based gas transfer parameterisation can be implemented and used. The updated version of the toolbox (version 3) and all documentation is now freely available.

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 (O3), aerosols) and terrestrial gaseous emissions could be taken up by the coastal seas.To address this, we present air–sea fluxes of acetone, acetaldehyde and dimethylsulfide (DMS) at the coastal Penlee Point Atmospheric Observatory (PPAO) in the South-West UK during the spring (Apr-May 2018). Fluxes are quantified 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 fetch-limited Plymouth Sound fed by two estuaries.Mean EC (± 1 standard error) fluxes of acetone, acetaldehyde and DMS from the open-water wind sector were ‑8.01±0.77, ‑1.55±1.44 and 4.67±0.56 μmol m-2 d-1 respectively (- sign indicates 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 terrestrially influenced Plymouth Sound wind sector showed respective fluxes of -12.93±1.37, -4.45±1.73 and 1.75±0.80 μmol m-2 d-1. The greater deposition fluxes of acetaldehyde and acetone within the Plymouth Sound were largely 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 freshwater 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 diffusive VOC fluxes calculated with a two-layer (TL) model of gas transfer using air/water concentrations. The calculated TL fluxes are largely consistent with our direct measurements in the directions and magnitudes of fluxes. Generally, the TL model predicted acetone and acetaldehyde fluxes that were ~12–33 % higher (greater deposition) than the EC measurements. This could be due to sea surface processes that produce these carbonyl compounds that were not accounted for by the TL technique.

The flow (flux) of climate critical gases, such as carbon dioxide (CO2), between the ocean and the atmosphere is a fundamental component of our climate and the biogeochemical development of the oceans. Therefore, the accurate calculation of these air-sea gas fluxes is critical if we are to monitor the health of our oceans and changes to our climate. FluxEngine is an open source software toolbox that allows users to easily perform calculations of air-sea gas fluxes from model, in-situ and Earth observation data. The original development and verification of the toolbox was described in a previous publication and the toolbox is already being used by scientists across multiple disciplines. The toolbox has now been considerably updated to allow its use as a Python library, to enable simplified installation, verification of its installation, to enable the handling of multiple sparingly soluble gases and greatly expanded functionality for supporting in situ dataset analyses. This new functionality for supporting in situ analyses includes user defined grids, time periods and projections, the ability to re-analyse in situ CO2 data to a common temperature dataset and the ability to easily calculate gas fluxes using in situ data from drifting buoys, fixed moorings and research cruises. Here we describe these new capabilities and then demonstrate their application through illustrative case studies. The first case study demonstrates the workflow for accurately calculating CO2 fluxes using in situ data from four research cruises from the Surface Ocean CO2 Atlas (SOCAT) database. The second case study shows that reanalysing an eight month time series of pCO2 data collected from a fixed station in the Baltic Sea can remove errors equal to 35 % of the net air-sea gas flux. The third case study demonstrates that biological surfactants could supress individual nitrous oxide sea-air gas fluxes by up to 13 %. The final case study illustrates how a dissipation-based gas transfer parameterisation can be implemented and used. The updated version of the toolbox (version 3) and all documentation is now freely available.

We present air–sea fluxes of carbon dioxide (CO2), methane (CH4), momentum, and sensible heat measured by the eddy covariance method from the recently established Penlee Point Atmospheric Observatory (PPAO) on the south-west coast of the United Kingdom. Measurements from the south-westerly direction (open water sector) were made at three different sampling heights (approximately 15, 18, and 27 m above mean sea level, a.m.s.l.), each from a different period during 2014–2015. At sampling heights ≥ 18 m a.m.s.l., measured fluxes of momentum and sensible heat demonstrate reasonable ( ≤ ±20 % in the mean) agreement with transfer rates over the open ocean. This confirms the suitability of PPAO for air–sea exchange measurements in shelf regions. Covariance air–sea CO2 fluxes demonstrate high temporal variability. Air-to-sea transport of CO2 declined from spring to summer in both years, coinciding with the breakdown of the spring phytoplankton bloom. We report, to the best of our knowledge, the first successful eddy covariance measurements of CH4 emissions from a marine environment. Higher sea-to-air CH4 fluxes were observed during rising tides (20 ± 3; 38 ± 3; 29 ± 6 µmole m−2 d−1 at 15, 18, 27 m a.m.s.l.) than during falling tides (14 ± 2; 22 ± 2; 21 ± 5 µmole m−2 d−1), consistent with an elevated CH4 source from an estuarine outflow driven by local tidal circulation. These fluxes are a few times higher than the predicted CH4 emissions over the open ocean and are significantly lower than estimates from other aquatic CH4 hotspots (e.g. polar regions, freshwater). Finally, we found the detection limit of the air–sea CH4 flux by eddy covariance to be 20 µmole m−2 d−1 over hourly timescales (4 µmole m−2 d−1 over 24 h).

Air-water CH4 and CO2 fluxes were directly measured using the eddy covariance technique at the Penlee Point Atmospheric Observatory on the southwest coast of the United Kingdom from September 2015 to August 2016. The high frequency, year-long measurements provide unprecedented detail into the variability of these Greenhouse Gas fluxes from seasonal to diurnal and to semi-diurnal timescales. Depending on the wind sector, fluxes measured at this site are indicative of air-water exchange in coastal seas as well as in an outer estuary. For the open water sector when winds were off the Atlantic Ocean, annual CH4 emission averaged ~ 0.05 mmol m−2 d−1. Open water CH4 flux was near zero in December and January, probably due to reduced biological production of CH4. At times of high rainfall and river flow rate, CH4 emission from the estuarine-influenced Plymouth Sound sector was several times higher than emission from the open water sector. The implied CH4 saturation, derived from the measured fluxes and a wind speed dependent gas transfer velocity parameterization, of over 1000 % in the Plymouth Sound is within range of in situ dissolved CH4 measurements near the mouth of the river Tamar. CO2 flux from the open water sector was generally from sea-to-air in autumn and winter and from air-to-sea in late spring and summer, with an annual mean flux of near zero. CO2 flux from the Plymouth Sound sector was more positive, consistent with a higher dissolved CO2 concentration in the estuarine waters. A diurnal signal in CO2 flux and implied dissolved pCO2 are clearly observed for the Plymouth Sound sector and also evident for the open water sector during biologically productive periods. These observations suggest that coastal CO2 efflux may be underestimated if the sampling strategy is limited to daytime only. Combining the fluxes with in situ dissolved pCO2 measurements within the flux footprints allows us to estimate the CO2 transfer velocity. The gas transfer velocity vs. wind speed relationship at this coastal location agrees reasonably well with previous open water parameterizations in the mean, but demonstrates considerable variability. We discuss the influences of biological productivity and bottom-driven turbulence on coastal air-water gas exchange.

Emissions of dimethylsulfide (DMS) from the polar oceans play a key role in atmospheric processes and climate. Therefore, it is important we increase our understanding of how DMS production in these regions may respond to environmental change. The polar oceans are particularly vulnerable to ocean acidification (OA). However, our understanding of the polar DMS response is limited to two studies conducted in Arctic waters, where in both cases DMS concentrations decreased with increasing acidity. Here, we report on our findings from seven summertime shipboard microcosm experiments undertaken in a variety of locations in the Arctic Ocean and Southern Ocean. These experiments reveal no significant effects of short term OA on the net production of DMS by planktonic communities. This is in contrast to identical experiments from temperate NW European shelf waters where surface ocean communities responded to OA with significant increases in dissolved DMS concentrations. A meta-analysis of the findings from both temperate and polar waters (n = 18 experiments) reveals clear regional differences in the DMS response to OA. We suggest that these regional differences in DMS response reflect the natural variability in carbonate chemistry to which the respective communities may already be adapted. Future temperate oceans could be more sensitive to OA resulting in a change in DMS emissions to the atmosphere, whilst perhaps surprisingly DMS emissions from the polar oceans may remain relatively unchanged. By demonstrating that DMS emissions from geographically distinct regions may vary in response to OA, our results may facilitate a better understanding of Earth's future climate. Our study suggests that the way in which processes that generate DMS respond to OA may be regionally distinct and this should be taken into account in predicting future DMS emissions and their influence on Earth's climate.

The aim of this research was to make the first depth profiles of the microbial assimilation of methanol carbon and its oxidation to carbon dioxide and use as an energy source from the microlayer to 1000 m. Some of the highest reported methanol oxidation rate constants of 0.5–0.6 d−1 were occasionally found in the microlayer and immediately underlying waters (10 cm depth), albeit these samples also showed the greatest heterogeneity compared to other depths down to 1000 m. Methanol uptake into the particulate phase was exceptionally low in microlayer samples, suggesting that any methanol utilised by microbes in this environment is for energy generation. The sea surface microlayer and 10 cm depth also showed a higher proportion of bacteria with a low DNA content, and bacterial leucine uptake rates in surface microlayer samples were either less than or the same as those in the underlying 10 cm layer. The average methanol oxidation and particulate rates were however statistically the same throughout the depths sampled, although the latter were highly variable in the near-surface 0.25–2 m compared to deeper depths. The statistically significant relationship demonstrated between uptake of methanol into particles and bacterial leucine incorporation suggests that many heterotrophic bacteria could be using methanol carbon for cellular growth. On average, methanol bacterial growth efficiency (BGEm) in the top 25 m of the water column is 6% and decreases with depth. Although, for microlayer and 10 cm-depth samples, BGEm is less than the near-surface 25–217 cm, possibly reflecting increased environmental UV stress resulting in increased maintenance costs, i.e. energy required for survival. We conclude that microbial methanol uptake rates, i.e. loss from seawater, are highly variable, particularly close to the seawater surface, which could significantly impact upon seawater concentrations and hence the air–sea flux.

Very short-lived halocarbons (VSLH) such as CH3I, CH2Br2 and CHBr3 provide an important source of reactive halogens to the atmosphere, however high spatial and seasonal variability in their ambient mixing ratios and sea-air fluxes gives rise to considerable uncertainty in global scale emission estimates. One solution to improve global flux estimates is to combine the multitude of individually published datasets to produce a database of collated global halocarbon observations. Some progress towards this has already been achieved through the HalOcAt (Halocarbons in the Ocean and Atmosphere) database initiative, but the absence of a common calibration scale for very short-lived halocarbons makes it difficult to distinguish true environmental variations from artefacts arising from differences between calibration methodologies. As such, the lack of inter-calibrations for both air and seawater measurements of very short-lived halocarbons has been identified as a major limitation to current estimations of the global scale impact of these reactive trace gases. Here we present the key findings from the first national UK inter-laboratory comparison for calibrations of the halocarbons CH3I, CH2Br2 and CHBr3. The aim of this inter-calibration was to provide transparency between halocarbon calibrations from major UK research institutions, an important step towards enabling all measurements from these institutions to be treated as one coherent integrated dataset for global source term parameterisations.