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Estuaries receive and process a large amount of particulate organic carbon (POC) prior to its export into coastal waters. Studying the origin of this POC is key to understanding the fate of POC and the role of estuaries in the global carbon cycle. Here, we evaluated the concentrations of POC, as well as particulate organic nitrogen (PON), and used stable carbon and nitrogen isotopes to assess their sources across 13 contrasting British estuaries during five different sampling campaigns over 1 year. We found a high variability in POC and PON concentrations across the salinity gradient, reflecting inputs, and losses of organic material within the estuaries. Catchment land cover appeared to influence the contribution of POC to the total organic carbon flux from the estuary to coastal waters, with POC contributions >36% in estuaries draining catchments with a high percentage of urban/suburban land, and

Dissolved inorganic carbon (DIC) fluxes from the land to ocean have been quantified for many rivers globally. However, CO2 fluxes to the atmosphere from inland waters are quantitatively significant components of the global carbon cycle that are currently poorly constrained. Understanding, the relative contributions of natural and human-impacted processes on the DIC cycle within catchments may provide a basis for developing improved management strategies to mitigate free CO2 concentrations in rivers and subsequent evasion to the atmosphere. Here, a large, internally consistent dataset collected from 41 catchments across Great Britain (GB), accounting for ∼36% of land area (∼83,997 km2) and representative of national land cover, was used to investigate catchment controls on riverine dissolved inorganic carbon (DIC), bicarbonate (HCO3−) and free CO2 concentrations, fluxes to the coastal sea and annual yields per unit area of catchment. Estimated DIC flux to sea for the survey catchments was 647 kt DIC yr−1 which represented 69% of the total dissolved carbon flux from these catchments. Generally, those catchments with large proportions of carbonate and sedimentary sandstone were found to deliver greater DIC and HCO3− to the ocean. The calculated mean free CO2 yield for survey catchments (i.e. potential CO2 emission to the atmosphere) was 0.56 t C km−2 yr−1. Regression models demonstrated that whilst river DIC (R2 = 0.77) and HCO3− (R2 = 0.77) concentrations are largely explained by the geology of the landmass, along with a negative correlation to annual precipitation, free CO2 concentrations were strongly linked to catchment macronutrient status. Overall, DIC dominates dissolved C inputs to coastal waters, meaning that estuarine carbon dynamics are sensitive to underlying geology and therefore are likely to be reasonably constant. In contrast, potential losses of carbon to the atmosphere via dissolved CO2, which likely constitute a significant fraction of net terrestrial ecosystem production and hence the national carbon budget, may be amenable to greater direct management via altering patterns of land use.

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 flux of terrigenous organic carbon through estuaries is an important and changing, yet poorly understood, component of the global carbon cycle. Using dissolved organic carbon (DOC) and fluorescence data from 13 British estuaries draining catchments with highly variable land uses, we show that land use strongly influences the fate of DOC across the land ocean transition via its influence on the composition and lability of the constituent dissolved organic matter (DOM). In estuaries draining peatland-dominated catchments, DOC was highly correlated with biologically refractory “humic-like” terrigenous material which tended to be conservatively transported along the salinity gradient. In contrast, there was a weaker correlation between DOC and DOM components within estuaries draining catchments with a high degree of human impact, that is, relatively larger percentage of arable and (sub)urban land uses. These arable and (sub)urban estuaries contain a high fraction of bioavailable “protein-like” material that behaved nonconservatively, with both DOC removals and additions occurring. In general, estuaries draining catchments with a high percentage of peatland (≥18%) have higher area-specific estuarine exports of DOC (>13 g C m−2 yr−1) compared to those estuaries draining catchments with a high percentage (≥46%) of arable and (sub)urban land uses (

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).

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.

The ability to routinely quantify global carbon dioxide (CO2) absorption by the oceans has become crucial: it provides a powerful constraint for establishing global and regional carbon (C) budgets, and enables identification of the ecological impacts and risks of this uptake on the marine environment. Advances in understanding, technology, and international coordination have made it possible to measure CO2 absorption by the oceans to a greater degree of accuracy than is possible in terrestrial landscapes. These advances, combined with new satellite‐based Earth observation capabilities, increasing public availability of data, and cloud computing, provide important opportunities for addressing critical knowledge gaps. Furthermore, Earth observation in synergy with in‐situ monitoring can provide the large‐scale ocean monitoring that is necessary to support policies to protect ocean ecosystems at risk, and motivate societal shifts toward meeting C emissions targets; however, sustained effort will be needed. In a nutshell: The oceans cover >70% of the Earth's surface and are critical for food supply and maintaining global climate Increasing carbon dioxide (CO2) absorption alters ocean chemistry and ecology, affecting marine ecosystems over both the short and long term Accurate estimates of CO2 absorption by the world's oceans provide a powerful constraint on carbon (C) budgets, and are needed to inform policies to motivate societal shifts toward reducing C emissions We review recent and foreseeable advances for studying oceanic CO2 absorption, explain why satellite‐based Earth observation is key to addressing existing knowledge gaps, and discuss how global monitoring is now both possible and necessary to support policy and conservation

Observations made within a cold filament in the Mauritanian upwelling system demonstrate that intense submesoscale circulations at the peripheral edges of the filament are likely responsible for anomalously high levels of observed primary productivity by resupplying nutrients to the euphotic zone. Measurements made on the shelf within the recently upwelled water reveal that primary production (PP) of 8.2 gC/m−2 day−1 was supported by nitrate concentrations (NC) of 8 mmol m−3. Towards the front that defined the edge of the filament containing the upwelled water as it was transported offshore, PP dropped to 1.6 gC m−2 day−1 whilst NC dropped to 5.5 mmol m−3. Thus, whilst the observed nutrients on the shelf accounted for 90% of new production, this value dropped to ∼60% near the filament’s front after accounting for vertical turbulent fluxes and Ekman pumping. We demonstrate that the N15 was likely to have been supplied at the front by submesoscale circulations that were directly measured as intense vertical velocities ⩾100 m day−1 by a drifting acoustic Doppler current profiler that crossed a submesoscale surface temperature front. At the same time, a recently released tracer was subducted out of the mixed layer within 24 h of release, providing direct evidence that the frontal circulations were capable of accessing the reservoir of nutrients beneath the pycnocline. The susceptibility of the filament edge to submesoscale instabilities was demonstrated by O(1) Rossby numbers at horizontal scales of 1–10 km. The frontal circulations are consistent with instabilities arising from a wind-driven nonlinear Ekman buoyancy flux generated by the persistent northerly wind stress that has a down-front component at the northern edge of the inshore section of the filament. The prevalence of submesoscale instabilities and their associated vertical circulations are proposed to be a key mechanism operating at sub-grid scales and sustaining new production throughout the upwelling system.

Since 1995 the Atlantic Meridional Transect program (AMT - www.amt-uk.org) has undertaken extensive measurements of oceanographic and atmospheric variables on a passage between the UK and destinations in the South Atlantic (Falkland Islands, Chile, Uruguay and South Africa). This program, which spans more than 100° of latitude, crosses a range of ecosystems from sub-polar to tropical, from eutrophic shelf seas and upwelling systems, to oligotrophic mid-ocean gyres (Fig. 1). The AMT was originally conceived to utilise the bi-annual passage of the RRS James Clark Ross (JCR) between its home-base in the UK and its field-base in the Falklands. This initial phase, from 1995 to 2000 was largely funded by the Plymouth Marine Laboratory (PML) and the Natural Environment Research Council (NERC) with additional support from NASA in order to test and ground-truth satellite algorithms of ocean colour (Aiken & Bale, 2000). The opportunities offered by this initiative meant that this series of repeated bi-annual cruises rapidly developed into a coordinated study of ocean biodiversity, biogeochemistry and ocean/atmosphere interactions. The second phase, between 2002 and 2006 was funded by a NERC consortium grant which is introduced and summarised in two manuscripts by Robinson (Robinson et al., 2009, Robinson et al., 2006) which form the introduction to special issues of Deep-Sea Research II. This phase utilised a hypothesis-led approach concerning the biogeochemistry of the different Atlantic Ocean provinces. In the third phase, from 2008 to present, funding from NERC was directed through the OCEANS2025 program and latterly through UK National Capability. During this phase, cruises switched from bi-annual to annual, taking place during the boreal autumn (austral spring). A summary of the annual and seasonal coverage of AMT cruises is given in Figure 2. Throughout the lifetime of the AMT program the objectives have evolved to address topical research questions whilst enabling the maintenance of a continuous set of observations relevant to global issues that are raised throughout the most recent IPCC assessment (Rhein et al., 2013) and UK environmental strategy.

We report the first measurements of surfactant activity (SA) in the sea surface microlayer (SML) and in sub-surface waters (SSW) at the ocean basin scale, for two Atlantic Meridional Transects (AMT) from 50°N to 50°S during 2014 and 2015. Northern hemisphere (NH) SA was significantly higher than southern hemisphere (SH) SA in the SML and in the SSW. SA enrichment factors (EF = SASML/SASSW) were also higher in the NH, for wind speeds up to ~13 m s-1, questioning a prior assertion that Atlantic Ocean wind speeds > 12 m s-1 poleward of 30°N and 30°S would preclude high EFs and showing the SML to be self-sustaining with respect to SA. Our results imply that surfactants exert a control on air-sea CO2 exchange across the whole North Atlantic CO2 sink region and that the contribution made by high wind, high latitude oceans to air-sea gas exchange globally should be re-examined.

Shelf seas play an important role in the global carbon cycle, absorbing atmospheric carbon dioxide (CO2) and exporting carbon (C) to the open ocean and sediments. The magnitude of these processes is poorly constrained, because observations are typically interpolated over multiple years. Here, we used 298500 observations of CO2 fugacity (fCO2) from a single year (2015), to estimate the net influx of atmospheric CO2 as 26.2 ± 4.7 Tg C yr−1 over the open NW European shelf. CO2 influx from the atmosphere was dominated by influx during winter as a consequence of high winds, despite a smaller, thermally-driven, air-sea fCO2 gradient compared to the larger, biologically-driven summer gradient. In order to understand this climate regulation service, we constructed a carbon-budget supplemented by data from the literature, where the NW European shelf is treated as a box with carbon entering and leaving the box. This budget showed that net C-burial was a small sink of 1.3 ± 3.1 Tg C yr−1, while CO2 efflux from estuaries to the atmosphere, removed the majority of river C-inputs. In contrast, the input from the Baltic Sea likely contributes to net export via the continental shelf pump and advection (34.4 ± 6.0 Tg C yr−1).

Shelf seas play an important role in the global carbon cycle, absorbing atmospheric carbon dioxide (CO2) and exporting carbon (C) to the open ocean and sediments. The magnitude of these processes is poorly constrained, because observations are typically interpolated over multiple years. Here, we used 298500 observations of CO2 fugacity (fCO2) from a single year (2015), to estimate the net influx of atmospheric CO2 as 26.2 ± 4.7 Tg C yr−1 over the open NW European shelf. CO2 influx from the atmosphere was dominated by influx during winter as a consequence of high winds, despite a smaller, thermally-driven, air-sea fCO2 gradient compared to the larger, biologically-driven summer gradient. In order to understand this climate regulation service, we constructed a carbon-budget supplemented by data from the literature, where the NW European shelf is treated as a box with carbon entering and leaving the box. This budget showed that net C-burial was a small sink of 1.3 ± 3.1 Tg C yr−1, while CO2 efflux from estuaries to the atmosphere, removed the majority of river C-inputs. In contrast, the input from the Baltic Sea likely contributes to net export via the continental shelf pump and advection (34.4 ± 6.0 Tg C yr−1).

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.

Methanol is ubiquitous in seawater and the most abundant oxygenated volatile organic compound (OVOC) in the atmosphere where it influences oxidising capacity and ozone formation. Marine methylotrophic bacteria utilise methanol in seawater both as an energy and/or growth substrate. This work represents the first fully resolved seasonal study of marine microbial methanol uptake dynamics. Rates of microbial methanol dissimilation in coastal surface waters of the UK varied between 0.7 – 11.2 nmol l-1 h-1 and reached a maximum in February. Rates of microbial methanol assimilation varied between 0.04 – 2.64 x 10-2 nmol l-1 h-1 and reached a maximum in August. Temporal variability in microbial methanol uptake rates shows that methanol assimilation and dissimilation display opposing seasonal cycles, although overall

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).

Physical oceanography is the study of physical conditions, processes and variables within the ocean, including temperature–salinity distributions, mixing of the water column, waves, tides, currents and air–sea interaction processes. Here we provide a critical review of how satellite sensors are being used to study physical oceanography processes at the ocean surface and its borders with the atmosphere and sea ice. The paper begins by describing the main sensor types that are used to observe the oceans (visible, thermal infrared and microwave) and the specific observations that each of these sensor types can provide. We then present a critical review of how these sensors and observations are being used to study: (i) ocean surface currents, (ii) storm surges, (iii) sea ice, (iv) atmosphere–ocean gas exchange and (v) surface heat fluxes via phytoplankton. Exciting advances include the use of multiple sensors in synergy to observe temporally varying Arctic sea ice volume, atmosphere–ocean gas fluxes, and the potential for four-dimensional water circulation observations. For each of these applications we explain their relevance to society, review recent advances and capability, and provide a forward look at future prospects and opportunities. We then more generally discuss future opportunities for oceanography-focused remote sensing, which includes the unique European Union Copernicus programme, the potential of the International Space Station and commercial miniature satellites. The increasing availability of global satellite remote-sensing observations means that we are now entering an exciting period for oceanography. The easy access to these high quality data and the continued development of novel platforms is likely to drive further advances in remote sensing of the ocean and atmospheric systems.

Models of the air-sea transfer velocity of gases may be either empirical or mechanistic. Extrapolations of empirical models to an unmeasured gas or to another water temperature can be erroneous if the basis of that extrapolation is flawed. This issue is readily demonstrated for the most well-known empirical gas transfer velocity models where the influence of bubble-mediated transfer, which can vary between gases, is not explicitly accounted for. Mechanistic models are hindered by an incomplete knowledge of the mechanisms of air-sea gas transfer. We describe a hybrid model that incorporates a simple mechanistic view—strictly enforcing a distinction between direct and bubble-mediated transfer—but also uses parameterizations based on data from eddy flux measurements of dimethyl sulphide (DMS) to calibrate the model together with dual tracer results to evaluate the model. This model underpins simple algorithms that can be easily applied within schemes to calculate local, regional, or global air-sea fluxes of gases.

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.

Methanol is a climate-active gas and the most abundant oxygenated volatile organic compound (OVOC) in the atmosphere and seawater. Marine methylotrophs are aerobic bacteria that utilise methanol from seawater as a source of carbon (assimilation) and/or energy (dissimilation). A few spatially limited studies have previously reported methanol oxidation rates in seawater; however, the basin-wide ubiquity of marine microbial methanol utilisation remains unknown. This study uniquely combines seawater 14C labelled methanol tracer studies with 16S rRNA pyrosequencing to investigate variability in microbial methanol dissimilation and known methanol-utilising bacteria throughout a meridional transect of the Atlantic Ocean between 47° N to 39° S. Microbial methanol dissimilation varied between 0.05 and 1.68 nmol L−1 h−1 in the top 200 m of the Atlantic Ocean and showed significant variability between biogeochemical provinces. The highest rates of methanol dissimilation were found in the northern subtropical gyre (average 0.99±0.41 nmol L−1 h−1), which were up to 8 times greater than other Atlantic regions. Microbial methanol dissimilation rates displayed a significant inverse correlation with heterotrophic bacterial production (determined using 3H-leucine). Despite significant depth stratification of bacterial communities, methanol dissimilation rates showed much greater variability between oceanic provinces compared to depth. There were no significant differences in rates between samples collected under light and dark environmental conditions. The variability in the numbers of SAR11 (16S rRNA gene sequences) were estimated to explain approximately 50 % of the changes in microbial methanol dissimilation rates. We estimate that SAR11 cells in the Atlantic Ocean account for between 0.3 % and 59 % of the rates of methanol dissimilation in Atlantic waters, compared to

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.

In 2014–5 the UK NERC sponsored an 18 month long Shelf Sea Biogeochemistry research programme which collected over 1500 nutrient and carbonate system samples across the NW European Continental shelf, one of the largest continental shelves on the planet. This involved the cooperation of 10 different Institutes and Universities, using 6 different vessels. Additional carbon dioxide (CO2) data were obtained from the underway systems on three of the research vessels. Here, we present and discuss these data across 9 ecohydrodynamic regions, adapted from those used by the EU Marine Strategy Framework Directive (MSFD). We observed strong seasonal and regional variability in carbonate chemistry around the shelf in relation to nutrient biogeochemistry. Whilst salinity increased (and alkalinity decreased) out from the near-shore coastal waters offshore throughout the year nutrient concentrations varied with season. Spatial and seasonal variations in the ratio of DIC to nitrate concentration were seen that could impact carbon cycling. A decrease in nutrient concentrations and a pronounced under-saturation of surface pCO2 was evident in the spring in most regions, especially in the Celtic Sea. This decrease was less pronounced in Liverpool Bay and to the North of Scotland, where nutrient concentrations remained measurable throughout the year. The near-shore and relatively shallow ecosystems such as the eastern English Channel and southern North Sea were associated with a thermally driven increase in pCO2 to above atmospheric levels in summer and an associated decrease in pH. Non-thermal processes (such as mixing and the remineralisation of organic material) dominated in winter in most regions but especially in the northwest of Scotland and in Liverpool Bay. The large database collected will improve understanding of carbonate chemistry over the North-Western European Shelf in relation to nutrient biogeochemistry, particularly in the context of climate change and ocean acidification.

We performed an annual study of oxygenated volatile organic compound (OVOC) seawater concentrations at a site off Plymouth, UK in the Western English Channel over the period of February 2011–March 2012. Acetone concentrations ranged from 2–10 nM (nanomole/L) in surface waters with a maximum observed in summer. Concentrations correlated positively with net shortwave radiation and UV light, suggestive of photochemically linked acetone production. We observed a clear decline in acetone concentrations below the mixed layer. Acetaldehyde varied between 4–37 nM in surface waters with higher values observed in autumn and winter. Surface concentrations of methanol ranged from 16–78 nM, but no clear annual cycle was observed. Methanol concentrations exhibited considerable inter-annual variability. We estimate consistent deposition to the sea surface for acetone and methanol but that the direction of the acetaldehyde flux varies during the year.

The sea-surface layer is the very upper part of the sea surface where reduced mixing leads to strong gradients in physical, chemical and biological properties1. This surface layer is naturally reactive, containing a complex chemistry of inorganic components and dissolved organic matter (DOM), the latter including amino acids, proteins, fatty acids, carbohydrates, and humic-type components,2 with a high proportion of functional groups such as carbonyls, carboxylic acids and aromatic moieties.3 The different physical and chemical properties of the surface of the ocean compared with bulk seawater, and its function as a gateway for molecules to enter the atmosphere or ocean phase, make this an interesting and important region for study. A number of chemical reactions are believed to occur on and in the surface ocean; these may be important or even dominant sources or sinks of climatically-active marine trace gases. However the sea surface, especially the top 1um to 1mm known as the sea surface microlayer (ssm), is critically under-sampled, so to date much of the evidence for such chemistry comes from laboratory and/or modeling studies. This review discusses the chemical and physical structure of the sea surface, mechanisms for gas transfer across it, and explains the current understanding of trace gas formation at this critical interface between the ocean and atmosphere.

The air-sea fluxes of methanol and acetone were measured concurrently using a proton-transfer-reaction mass spectrometer (PTR-MS) with the eddy covariance (EC) technique during the High Wind Gas Exchange Study (HiWinGS) in 2013. The seawater concentrations of these compounds were also measured twice daily with the same PTR-MS coupled to a membrane inlet. Dissolved concentrations near the surface ranged from 7 to 28 nM for methanol and from 3 to 9 nM for acetone. Both gases were consistently transported from the atmosphere to the ocean as a result of their low sea surface saturations. The largest influxes were observed in regions of high atmospheric concentrations and strong winds (up to 25 m s−1). Comparison of the total air-sea transfer velocity of these two gases (Ka), along with the in situ sensible heat transfer rate, allows us to constrain the individual gas transfer velocity in the air phase (ka) and water phase (kw). Among existing parameterizations, the scaling of ka from the COARE model is the most consistent with our observations. The kw we estimated is comparable to the tangential (shear driven) transfer velocity previously determined from measurements of dimethyl sulfide. Lastly, we estimate the wet deposition of methanol and acetone in our study region and evaluate the lifetimes of these compounds in the surface ocean and lower atmosphere with respect to total (dry plus wet) atmospheric deposition.

We present air–sea fluxes of oxygenated volatile organics compounds (OVOCs) quantified by eddy covariance (EC) during the Atlantic Meridional Transect cruise in 2012. Measurements of acetone, acetaldehyde, and methanol in air as well as in water were made in several different oceanic provinces and over a wide range of wind speeds (1–18 m s−1). The ocean appears to be a net sink for acetone in the higher latitudes of the North Atlantic but a source in the subtropics. In the South Atlantic, seawater acetone was near saturation relative to the atmosphere, resulting in essentially zero net flux. For acetaldehyde, the two-layer model predicts a small oceanic emission, which was not well resolved by the EC method. Chemical enhancement of air–sea acetaldehyde exchange due to aqueous hydration appears to be minor. The deposition velocity of methanol correlates linearly with the transfer velocity of sensible heat, confirming predominant airside control. We examine the relationships between the OVOC concentrations in air as well as in water, and quantify the gross emission and deposition fluxes of these gases.

[1] Oceanic methanol, acetaldehyde, and acetone concentrations were measured during an Atlantic Meridional Transect (AMT) cruise from the UK to Chile (49°N to 39°S) in 2009. Methanol (48–361 nM) and acetone (2–24 nM) varied over the track with enrichment in the oligotrophic Northern Atlantic Gyre. Acetaldehyde showed less variability (3–9 nM) over the full extent of the transect. These oxygenated volatile organic compounds (OVOCs) were also measured subsurface, with methanol and acetaldehyde mostly showing homogeneity throughout the water column. Acetone displayed a reduction below the mixed layer. OVOC concentrations did not consistently correlate with primary production or chlorophyll-a levels in the surface Atlantic Ocean. However, we did find a novel and significant negative relationship between acetone concentration and bacterial leucine incorporation, suggesting that acetone might be removed by marine bacteria as a source of carbon. Microbial turnover of both acetone and acetaldehyde was confirmed. Modeled atmospheric data are used to estimate the likely air-side OVOC concentrations. The direction and magnitude of air-sea fluxes vary for all three OVOCs depending on location. We present evidence that the ocean may exhibit regions of acetaldehyde under-saturation. Extrapolation suggests that the Atlantic Ocean represents an overall source of these OVOCs to the atmosphere at 3, 3, and 1 Tg yr−1 for methanol, acetaldehyde, and acetone, respectively.

[1] The biogeochemistry of oxygenated volatile organic compounds (OVOCs) like methanol, acetaldehyde, and acetone in marine waters is poorly understood. We report the first in situ gross production rates for methanol, acetaldehyde, and acetone of 49–103, 25–98, and 2–26 nmol L−1 d−1 over contrasting areas of marine productivity, including oligotrophic gyres and eutrophic upwellings. Photochemical production estimates are mostly negligible for methanol, up to 68% for acetaldehyde and up to 100% of gross production rates for acetone. Microbial surface OVOC oxidation to CO2 accounts for between 10–50% and 0.5–13% of the methanol and acetone losses, respectively, but largely control acetaldehyde concentrations (49–100%). Biological lifetimes in a coastal upwelling vary between ≤1 day for acetaldehyde, to approximately 7 days for methanol and up to ~80 days for acetone. In open oceanic environments, the lifetime of acetaldehyde ranges between 2 and 5 h, compared to 10–26 days for methanol and 5–55 days for acetone.

Oxygenated volatile organic compounds (OVOCs) in the atmosphere are precursors to peroxy acetyl nitrate (PAN), affect the tropospheric ozone budget, and in the remote marine environment represent a significant sink of the hydroxyl radical (OH). The sparse observational database for these compounds, particularly in the tropics, contributes to a high uncertainty in their emissions and atmospheric significance. Here, we show measurements of acetone, methanol, and acetaldehyde in the tropical remote marine boundary layer made between October 2006 and September 2011 at the Cape Verde Atmospheric Observatory (CVAO) (16.85° N, 24.87° W). Mean mixing ratios of acetone, methanol, and acetaldehyde were 546 ± 295 pptv, 742 ± 419 pptv, and 428 ± 190 pptv, respectively, averaged from approximately hourly values over this five-year period. The CAM-Chem global chemical transport model reproduced annual average acetone concentrations well (21% overestimation) but underestimated levels by a factor of 2 in autumn and overestimated concentrations in winter. Annual average concentrations of acetaldehyde were underestimated by a factor of 10, rising to a factor of 40 in summer, and methanol was underestimated on average by a factor of 2, peaking to over a factor of 4 in spring. The model predicted summer minima in acetaldehyde and acetone, which were not apparent in the observations. CAM-Chem was adapted to include a two-way sea-air flux parametrization based on seawater measurements made in the Atlantic Ocean, and the resultant fluxes suggest that the tropical Atlantic region is a net sink for acetone but a net source for methanol and acetaldehyde. Inclusion of the ocean fluxes resulted in good model simulations of monthly averaged methanol levels although still with a 3-fold underestimation in acetaldehyde. Wintertime acetone levels were better simulated, but the observed autumn levels were more severely underestimated than in the standard model. We suggest that the latter may be caused by underestimated terrestrial biogenic African primary and/or secondary OVOC sources by the model. The model underestimation of acetaldehyde concentrations all year round implies a consistent significant missing source, potentially from secondary chemistry of higher alkanes produced biogenically from plants or from the ocean. We estimate that low model bias in OVOC abundances in the remote tropical marine atmosphere may result in up to 8% underestimation of the global methane lifetime due to missing model OH reactivity. Underestimation of acetaldehyde concentrations is responsible for the bulk (∼70%) of this missing reactivity.

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.

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.

Methanol is the second most abundant organic gas in the atmosphere after methane, and is ubiquitous in the troposphere. It plays a significant role in atmospheric oxidant chemistry and is biogeochemically active. Large uncertainties exist about whether the oceans are a source or sink of methanol to the atmosphere. Even less is understood about what reactions in seawater determine its concentration, and hence flux across the sea surface interface. We report here concentrations of methanol between 151–296 nM in parts of the oligotrophic North Atlantic, with corresponding microbial uptake rates between 2–146 nM d−1, suggesting turnover times as low as 1 day (1–25 days) in surface waters of the oligotrophic tropical North East Atlantic. Methanol is mainly (≥97%) used by microbes for obtaining energy in oligotrophic regions, which contrasts with shelf and coastal areas where between 20–50% can be used for cell growth. Comparisons of microbial methanol oxidation rates with parallel determinations of bacterial leucine uptake suggest that methanol contributes on average 13% to bacterial carbon demand in the central northern Atlantic gyre (maximum of 54%). In addition, the contribution that methanol makes to bacterial carbon demand varies as a power function of chlorophyll a concentrations; suggesting for concentrations −1 that methanol can make a significant contribution to bacterial carbon demand. However, our low air to sea methanol flux estimates of 7.2–13 μmol m−2 d−1 suggest that the atmosphere is not a major methanol source. We conclude that there must be a major, as yet unidentified, in situ oceanic methanol source in these latitudes which we suggest is sunlight driven decomposition of organic matter.

This document is a supplement to “Physical Exchanges at the Air–Sea Interface: UK–SOLAS Field Measurements,” by Ian M. Brooks, Margaret J. Yelland, Robert C. Upstill-Goddard, Philip D. Nightingale, Steve Archer, Eric d’Asaro, Rachael Beale, Cory Beatty, Byron Blomquist, A. Anthony Bloom, Barbara J. Brooks, John Cluderay, David Coles, John Dacey, Michael DeGrandpre, Jo Dixon, William M. Drennan, Joseph Gabriele, Laura Goldson, Nick Hardman-Mountford, Martin K. Hill, Matt Horn, Ping-Chang Hsueh, Barry Huebert, Gerrit de Leeuw, Timothy G. Leighton, Malcolm Liddicoat, Justin J. N. Lingard, Craig McNeil, James B. McQuaid, Ben I. Moat, Gerald Moore, Craig Neill, Sarah J. Norris, Simon O’Doherty, Robin W. Pascal, John Prytherch, Mike Rebozo, Erik Sahlee, Matt Salter, Ute Schuster, Ingunn Skjelvan, Hans Slagter, Michael H. Smith, Paul D. Smith, Meric Srokosz, John A. Stephens, Peter K. Taylor, Maciej Telszewski, Roisin Walsh, Brian Ward, David K. Woolf, Dickon Young, and Henk Zemmelink (Bull. Amer. Meteor. Soc., 90, 629–644) • ©2009 American Meteorological Society • Corresponding author: Ian M. Brooks, Institute for Climate and Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds LS2 9JT, United Kingdom • E-mail: i.brooks@see.leeds.ac.uk • DOI:10.1175/2008BAMS2578.2

We present the first reported measurements of volatile iodocarbon production by biogenic marine aggregates. Iodomethane (CH3I), iodoethane (C2H5I), 2-iodopropane (CH3CHICH3), and 1-iodopropane (CH3CH2CH2I) concentrations were determined in incubations of aggregates formed by concentrating the >53 mu m fraction of the plankton during a field campaign in the Celtic Sea. All four iodocarbons increased significantly in concentration in the aggregate incubations relative to filtered seawater controls. Maximum production rates ranged from 0.01 pmol L-1 h(-1) for CH3CHICH3 to 0.31 pmol L-1 h(-1) for C2H5I. Accompanying pheopigment and bacterial heterotrophic production suggest that the processes taking place on the aggregates studied were a good representation of those known to occur on natural marine particles. We also report iodocarbon production rates observed in natural marine aggregates, including a diatom mucilage collected in the Celtic Sea and phytodetritus sampled from Kongsfjord in the Arctic. Detrital particles could be hotspots of iodocarbon production in the marine environment.

This study explores the changes in the surface water fugacity of carbon dioxide ( f CO 2 ) and biological carbon uptake in two Southern Ocean iron fertilisation experiments with different hydrographic regimes. The Southern Ocean Iron Release Experiment (SOIREE) experiment was carried out south of the Antarctic Polar Front (APF) at 61°S, 141°E in February 1999 in a stable hydrographic setting. The EisenEx experiment was conducted in a cyclonic eddy north of the APF at 48°S, 21°E in November 2000 and was characterised by a rapid succession of low to storm-force wind speeds and dynamic hydrographic conditions. The iron additions promoted algal blooms in both studies. They alleviated algal iron limitation during the 13-day SOIREE experiment and probably during the first 12 days of EisenEx. The f CO 2 in surface water decreased at a constant rate of 3.8 μatm day −1 from 4 to 5 days onwards in SOIREE. The f CO 2 reduction was 35 μatm after 13 days. The evolution of surface water f CO 2 in the iron-enriched waters (or ‘patch’) displayed a saw tooth pattern in EisenEx, in response to algal carbon uptake in calm conditions and deep mixing and horizontal dispersion during storms. The maximum f CO 2 reduction was 18–20 μatm after 12 and 21 days with lower values in between. The iron-enriched waters in EisenEx absorbed four times more atmospheric CO 2 than in SOIREE between 5 and 12 days, as a result of stronger winds. The total biological uptake of inorganic carbon across the patch was 1389 ton C (±10%) in SOIREE and 1433 ton C (±27%) in EisenEx after 12 days (1 ton=10 6 g). This similarity probably reflects the comparable size of the iron additions, as well as algal growth at a similar near-maximum growth rate in these regions. The findings imply that the different mixing regimes had less effect on the overall biological carbon uptake across the iron-enriched waters than suggested by the evolution of f CO 2 in surface water.

Notre etude de modelisation vise a placer dans un cycle annuel nos connaissances de la biogeochimie du sulfure de dimethyle (DMS), un gaz qui affecte le climat, dans les eaux marines superficielles. Nous avons incorpore les processus impliques dans la production et le sort du DMS et de son precurseur le β-dimethylsulfoniopropionate (DMSP), un produit de synthese du phytoplancton, dans le modele ERSEM (« European Regional Seas Ecosystem Model »), un modele physique, complexe, unidimensionel et couple de l'ecosysteme et dans le modele GOTM (« General Ocean Turbulence Model »). Nous avons ainsi mis au point un modele de la biogeochimie du DMS applique a des donnees de 1989 provenant d'un site a stratification saisonniere de la mer du Nord. Nous l'avons valide avec des donnees de concentrations de nutriments, de biomasses biologiques, de production biologique, de concentrations de DMS et de DMSP et de flux de DMS de la mer a l'atmosphere obtenues en 1989 dans le cadre du Projet de la mer du Nord (« North Sea Project »). Les resultats de cette validation demontrent que des modeles complexes de l'ecosysteme, combines a un reseau complet des processus qui controlent la production et le sort du DMSP et du DMS, peuvent representer de facon exacte la biogeochimie du DMS. Le modele fournit des perspectives interessantes sur l'impact du forcage physique, qui varie d'une saison a l'autre, sur les contributions relatives des divers processus particuliers a la production du DMS et a son passage de la mer a l'atmosphere.

This paper presents an overview of dimethyl sulphide biogeochemistry within a coccolithophore bloom (DISCO), an integrated, multidisciplinary Lagrangian process study of the routes, rates and controls on the biogeochemical cycling of dimethyl sulphide (DMS) within a growing bloom of the coccolithophorid alga, Emiliania huxleyi . The Lagrangian study took place between 16 and 26 June 1999 in the northern North Sea. It was preceded by an 8-d survey of ∼52,000 km 2 of the region to locate an E. huxleyi bloom suitable for study. Although not originally planned, the survey was carried out because heavy cloud cover precluded use of remote sensing to locate a suitable bloom. E. huxleyi blooms, typically common in the region during mid-summer, were unusually sparse in the study area. The bloom chosen for the process study was initially centred ∼58°56′N 02°52′E, and a 40-km 2 patch of water was labelled for study with ∼30 g sulphur hexafluoride (SF 6 ) on 16 June. The original patch was reinfused with further SF 6 on 24 June. During the process study, the SF 6 -labelled patch moved in a south-easterly direction and the study ended when the patch subducted underneath less dense Norwegian coastal water. The process study comprised analyses of the time-varying biological, optical and physical properties of the patch as well as studies of DMS, dimethylsulphonioproprionate (DMSP), dimethylsulphoxide, nutrients, halocarbons, methylamines, carbon monoxide, dissolved organic carbon, and total dissolved nitrogen. The role of viruses, bacteria, phytoplankton, microzooplankton, and mesozooplankton, together with the dynamics of primary, new and bacterial production, plankton respiration, microzooplankton grazing, and sedimentation, were studied in relation to the biogeochemical cycling of DMS. Although the coccolithophore bloom water exhibited high optical backscatter, the algal community present was highly heterogeneous. Flagellates other than E. huxleyi were found to dominate the phytoplankton. A budget of the DMSP pools suggested that E. huxleyi accounted for only 13% of the stocks of particulate DMSP, showing that in this “ E. huxleyi bloom”, taxa other than E. huxleyi were important sources of DMSP. In this young bloom, particulate and dissolved DMSP and DMS concentrations averaged 1360, 155 and 60 μM m −2 , respectively, in the surface mixed layer. Surface-water particulate DMSP concentrations increased during the study at a net rate of 13% d −1 , as did concentrations of phytoplankton including E. huxleyi , confirming that the bloom was developing. Nutrient conditions were low in the mixed layer throughout the study, maintained by a strong pycnocline across which nitrate upflux was estimated to be ∼2 nM dm −3 d −1 . Primary production was fuelled by regenerated nutrients, although nitrification rates in surface waters were found to be significant. Microzooplankton grazing accounted for 91% of the particulate DMSP degradation and was considered to be a major control on the DMSP concentration. Vigorous microzooplankton grazing together with rapid uptake of dissolved DMSP by bacteria suggest that microzooplankton were the main route for the production of dissolved DMSP. The bacterial community was dominated by one taxon, an α proteobacteria related to Roseobacter that satisfied its entire sulphur demand by metabolising dissolved DMSP. Bacteriogenic DMS production amounted to 2 nM d −1 and was considered the main route for DMS production. In vitro DMSPlyase activity was very high, but there was little evidence for high in situ activity. Over the study period, DMS flux to the atmosphere was estimated to be 7 μM m −2 d −1 , equivalent to ∼1% of the DMSP sulphur produced in the surface mixed layer. A budget for DMS cycling in the upper mixed layer is presented based on the analytical and experimental measurements made in the DISCO study.

This study describes the routes and rates of transformation of dimethylsulphoniopropionate (DMSP) to dimethyl sulphide (DMS) in a phytoplankton bloom in the northern North Sea (59°N 2°E). A region on the edge of the high reflectance waters that characterised the bloom was labelled with SF6-tracer and tracked for 6 days. Within the framework of this Lagrangian experiment, it was possible to compile a comprehensive budget of the transformation of DMSP to DMS in the surface mixed layer of 15–30 m depth and a subsurface layer that extended to ⩾40 m. As a basis to the synthesis of the DMS(P) biogeochemistry, an attempt was made to accurately constrain DMS emissions from the Lagrangian water mass. Included in the study is a comparison of estimates of the transfer velocity and DMS sea to air flux derived from two well established and two recently introduced parameterisations. The two recent approaches encouragingly gave similar rates of total DMS sea to air flux of 1.60 mg S m−2 over the 6-day experimental period, and this value was intermediate to values derived from the two more routinely used approaches. The DMS sea to air flux was equivalent in terms of sulphur, to 10% of the DMS production and 1.3% of the particulate DMSP (DMSPp) production in the surface layer over the 6 days. Bacterial consumption accounted for the majority of DMS removal in both surface (62–82%) and subsurface layers (average 98%) and DMS concentrations decreased over the 6 days, despite increasing DMS production. Microzooplankton were the main agents of the transformation of DMSPp to the dissolved phase but little DMS appeared to be produced directly by the grazers. Instead, bacteria rapidly turned over the dissolved DMSP (DMSPd) made available by the grazers. An upper limit of 17% of the DMSPd consumed by bacteria in the surface layer was cleaved to DMS over the 6 days. Lower transformation efficiencies of ∼6% were estimated for the subsurface layer. An ecosystem model incorporating DMS(P) biogeochemistry was developed on the basis of the empirical data. Simple sensitivity analyses were employed to demonstrate the importance of both microzooplankton and bacterial metabolism in controlling the yield of DMS from DMSP production and hence, the DMS sea to air flux. Greater yields of DMS are likely to occur when DMSPp is transformed directly to DMS, in this case due to grazing, than when transformed to DMSPd and subsequently cleaved to DMS by bacterial activity. The point of DMS production in the DMSPp to DMS transformation pathway is likely to alter in relation to phytoplankton bloom progression and with season. The complex interaction amongst heterotrophic processes that control DMS concentrations suggests that attempts to predict global DMS flux may need to couple comprehensive ecosystem models of the type used in this study, to general circulation models.

One of the key steps towards predicting dimethyl sulphide (DMS) emissions to the atmosphere is to understand the production and fate of its precursor, dimethylsulphoniopropionate (DMSP). This study used the framework of a SF 6 -Lagrangian experiment lasting 6 days, to examine the production and turnover of particulate DMSP (DMSPp) within a developing phytoplankton bloom characterised by abundant Emiliania huxleyi . Detailed information on the composition of the phytoplankton community and literature-derived estimates of cell DMSP content were used to partition DMSPp between 6 taxonomic groups. E. huxleyi was estimated to contribute an average of only 16% and 9% of the DMSPp standing stocks in surface and subsurface layers of the water column, respectively. Other phototrophs, including non-lithed nanoflagellates and dinoflagellates, in particular Prorocentrum minimum, made up a substantial proportion of the DMSPp, especially in the subsurface layer. The Lagrangian approach allowed a direct estimate of the net production of DMSPp, chlorophyll a and the 6 phytoplankton taxonomic groups in the surface layer. The net specific accumulation rate of DMSPp was 0.129 day −1 , equivalent to a net production of DMSPp over the 6 days of 37.3 nM averaged through the surface-layer depth. The net phytoplankton growth rate in terms of chlorophyll a was similar, at 0.108 day −1 . However, not all the phytoplankton showed a net growth during the 6 days, indicating that only certain taxa were responsible for the increases in DMSP and chlorophyll a . A significant relationship between 14 C primary production measurements and the potential production of DMSPp derived from dilution experiments was used to estimate an integrated ‘gross’ production and loss rate of DMSPp for the surface mixed layer. High DMSPp production rates were closely matched by high DMSPp loss rates. Ingestion by microzooplankton appeared to be the major cause of DMSPp loss, accounting for an average of 91% of the DMSPp disappearance. A large proportion of the ingested DMSPp was thought to be released as dissolved DMSP rather than DMS. An estimate of the total DMS flux to the atmosphere was equivalent to only 1.3% of the ‘gross’ DMSPp production in the surface layer during the developing phase of the phytoplankton bloom covered by this experiment. Other processes known to cause DMSP release from phytoplankton, such as viral lysis and senescence, may have become more important if the phytoplankton community had reached higher concentrations and/or encountered more growth-limiting conditions. However, in the present experiment horizontal and vertical mixing appeared to play a major role in determining the fate of the SF 6 -labelled water, and hence the progression of the phytoplankton community.

Acetone is an important oxygenated volatile organic compound in the troposphere where it influences the oxidising capacity of the atmosphere. However, the air-sea flux is not well quantified, in part due to a lack of knowledge regarding which processes control oceanic concentrations, and, specifically whether microbial oxidation to CO2 represents a significant loss process. We demonstrate that 14C labelled acetone can be used to determine microbial oxidation to 14CO2. Linear microbial rates of acetone oxidation to CO2 were observed for between 0.75-3.5 hours at a seasonally eutrophic coastal station located in the western English Channel (L4). A kinetic experiment in summer at station L4 gave a Vmax of 4.1 pmol L-1 h-1, with a Km constant of 54 pM. We then used this technique to obtain microbial acetone loss rates ranging between 1.2-42 pmol L-1 h-1 (monthly averages) over an annual cycle at L4, with maximum rates observed during winter months. The biological turnover time of acetone (in situ concentration divided by microbial oxidation rate) in surface waters varied from ~3 days in February 2011, when in situ concentrations were 3 ± 1 nM, to >240 days in June 2011, when concentrations were more than 2 fold higher at 7.5 ± 0.7 nM. These relatively low marine microbial acetone oxidation rates, when normalised to in situ concentrations, suggest that marine microbes preferentially utilise other oxygenated volatile organic compounds such as methanol and acetaldehyde.

Many of the reactive trace gases detected in the atmosphere are both emitted from and deposited to the global oceans via exchange across the air–sea interface. The resistance to transfer through both air and water phases is highly sensitive to physical drivers (waves, bubbles, films, etc.), which can either enhance or suppress the rate of diffusion. In addition to outlining the fundamental processes controlling the air–sea gas exchange, the authors discuss these drivers, describe the existing parameterizations used to predict transfer velocities, and summarize the novel techniques for measuring in situ exchange rates. They review trace gases that influence climate via radiative forcing (greenhouse gases), those that can alter the oxidative capacity of the atmosphere (nitrogen- and sulfur-containing gases), and those that impact ozone levels (organohalogens), both in the troposphere and stratosphere. They review the known biological and chemical routes of production and destruction within the water column for these gases, whether the ocean acts as a source or sink, and whether temporal and spatial variations in saturation anomalies are observed. A current estimate of the marine contribution to the total atmospheric flux of these gases, which often highlights the significance of the oceans in biogeochemical cycling of trace gases, is provided, and how air–sea gas fluxes may change in the future is briefly assessed.

We describe the use of sulpho rhodamine G (SG) and rhodamine WT (WT) as oceanographic tracers in tidally active waters of the southeastern North Sea. Ten kilograms of SG and 5 kg of WT dissolved in 1,000 liters of sea water were released to produce an initial tracer patch ;10 3; 0.5 km. Tracer dispersal was monitored for 11 d by high-performance liquid chromatography analysis of samples collected close to the patch center. The patch center was initially identified during surveys for sulfur hexafluoride released simultaneously, and its position was subsequently confirmed by use of a two-dimensional tracer dispersion model. Temporal changes in the SG/WT ratio were undetectable, so photolytic tracer losses were not directly quantified. A simple photolysis model was used to correct to conservative behavior for WT. Results are compared with the dispersal of spores of Bacillus globigii var. niger released simultaneously. Photolytic tracer pairs are ideally suited to tracer experiments in unconstrained water masses.

The production rates of a range of low molecular weight halogenated organics have been determined in cultures of five temperate species of macroalgae collected from the north coast of Norfolk, England. Compounds studied included CH3Br, the chlorinated organics CH3Cl, CH2Cl2 and CHCl3, and the iodinated organics CH3I, C2H5I, and CH2ClI. Measurements of a wider range of halocarbon concentrations in an isolated rockpool and in air over the seaweed bed were also conducted to evaluate the local impact of the seaweeds on halocarbon concentrations in the natural environment. Estimates for the global emissions of some of the key halogenated compounds from macroalgae have been derived. In general macrophytes appear not to be globally significant producers of the particular halocarbons studied. In coastal regions, however, the impact on local atmospheric composition and chemistry could be greater.