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Human activities are changing the Arctic environment at an unprecedented rate resulting in rapid warming, freshening, sea ice retreat and ocean acidification of the Arctic Ocean. Trace gases such as nitrous oxide (N2O) and methane (CH4) play important roles in both the atmospheric reactivity and radiative budget of the Arctic and thus have a high potential to influence the region’s climate. However, little is known about how these rapid physical and chemical changes will impact the emissions of major climate-relevant trace gases from the Arctic Ocean. The combined consequences of these stressors present a complex combination of environmental changes which might impact on trace gas production and their subsequent release to the Arctic atmosphere. Here we present our current understanding of nitrous oxide and methane cycling in the Arctic Ocean and its relevance for regional and global atmosphere and climate and offer our thoughts on how this might change over coming decades. Supplementary Information The online version contains supplementary material available at 10.1007/s13280-021-01633-8.

Dimethyl sulphide (DMS) and carbon monoxide (CO) are climate-relevant trace gases that play key roles in the radiative budget of the Arctic atmosphere. Under global warming, Arctic sea ice retreats at an unprecedented rate, altering light penetration and biological communities, and potentially affect DMS and CO cycling in the Arctic Ocean. This could have socio-economic implications in and beyond the Arctic region. However, little is known about CO production pathways and emissions in this region and the future development of DMS and CO cycling. Here we summarize the current understanding and assess potential future changes of DMS and CO cycling in relation to changes in sea ice coverage, light penetration, bacterial and microalgal communities, pH and physical properties. We suggest that production of DMS and CO might increase with ice melting, increasing light availability and shifting phytoplankton community. Among others, policy measures should facilitate large-scale process studies, coordinated long term observations and modelling efforts to improve our current understanding of the cycling and emissions of DMS and CO in the Arctic Ocean and of global consequences.

Air–sea carbon dioxide ( CO2 ) flux is often indirectly estimated by the bulk method using the air–sea difference in CO2 fugacity ( Δf CO2 ) and a parameterisation of the gas transfer velocity ( K ). Direct flux measurements by eddy covariance (EC) provide an independent reference for bulk flux estimates and are often used to study processes that drive K . However, inherent uncertainties in EC air–sea CO2 flux measurements from ships have not been well quantified and may confound analyses of K . This paper evaluates the uncertainties in EC CO2 fluxes from four cruises. Fluxes were measured with two state-of-the-art closed-path CO2 analysers on two ships. The mean bias in the EC CO2 flux is low, but the random error is relatively large over short timescales. The uncertainty (1 standard deviation) in hourly averaged EC air–sea CO2 fluxes (cruise mean) ranges from 1.4 to 3.2 mmol m - 2 d - 1 . This corresponds to a relative uncertainty of ∼ 20 % during two Arctic cruises that observed large CO2 flux magnitude. The relative uncertainty was greater ( ∼ 50 %) when the CO2 flux magnitude was small during two Atlantic cruises. Random uncertainty in the EC CO2 flux is mostly caused by sampling error. Instrument noise is relatively unimportant. Random uncertainty in EC CO2 fluxes can be reduced by averaging for longer. However, averaging for too long will result in the inclusion of more natural variability. Auto-covariance analysis of CO2 fluxes suggests that the optimal timescale for averaging EC CO2 flux measurements ranges from 1 to 3 h, which increases the mean signal-to-noise ratio of the four cruises to higher than 3. Applying an appropriate averaging timescale and suitable Δf CO2 threshold (20 µatm ) to EC flux data enables an optimal analysis of K .

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 CO2 between the atmosphere and the ocean is often estimated as the air–sea gas concentration difference multiplied by the gas transfer velocity (K660). The first order driver for K660 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 K660. In this study we measured K660 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 CO2 using a Segmented Flow Coil Equilibrator system. GTE varied by 20% during the transect, was distinct in different water masses, and related to K660. At a moderate wind speed of 7 m s−1, K660 associated with high GTE exceeded K660 with low GTE by 30% in the mean. The sensitivity of K660 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 K660. Neglecting these variations could result in biases in the computed air–sea CO2 fluxes.

This work evaluates the sensitivity of CO 2 air–sea gas exchange in a coastal site to four different model system configurations of the 1D coupled hydrodynamic–ecosystem model GOTM–ERSEM, towards identifying critical dynamics of relevance when specifically addressing quantification of air–sea CO 2 exchange. The European Sea Regional Ecosystem Model (ERSEM) is a biomass and functional group-based biogeochemical model that includes a comprehensive carbonate system and explicitly simulates the production of dissolved organic carbon, dissolved inorganic carbon and organic matter. The model was implemented at the coastal station L4 (4 nm south of Plymouth, 50°15.00’N, 4°13.02’W, depth of 51 m). The model performance was evaluated using more than 1500 hydrological and biochemical observations routinely collected at L4 through the Western Coastal Observatory activities of 2008—-2009. In addition to a reference simulation (A), we ran three distinct experiments to investigate the sensitivity of the carbonate system and modeled air–sea fluxes to (B) the sea-surface temperature (SST) diurnal cycle and thus also the near-surface vertical gradients, (C) biological suppression of gas exchange and (D) data assimilation using satellite Earth observation data. The reference simulation captures well the physical environment (simulated SST has a correlation with observations equal to 0.94 with a p> 0.95). Overall, the model captures the seasonal signal in most biogeochemical variables including the air–sea flux of CO 2 and primary production and can capture some of the intra-seasonal variability and short-lived blooms. The model correctly reproduces the seasonality of nutrients (correlation > 0.80 for silicate, nitrate and phosphate), surface chlorophyll-a (correlation > 0.43) and total biomass (correlation > 0.7) in a two year run for 2008–2009. The model simulates well the concentration of DIC, pH and in-water partial pressure of CO 2 (pCO 2 ) with correlations between 0.4–0.5. The model result suggest that L4 is a weak net source of CO 2 (0.3–1.8 molCm − 2 year − 1 ). The results of the three sensitivity experiments indicate that both resolving the temperature profile near the surface and assimilation of surface chlorophyll-a significantly impact the skill of simulating the biogeochemistry at L4 and all of the carbonate chemistry related variables. These results indicate that our forecasting ability of CO 2 air–sea flux in shelf seas environments and their impact in climate modeling should consider both model refinements as means of reducing uncertainties and errors in any future climate projections.

A comprehensive in situ dataset of chlorophyll a (Chl a; N = 18,001), net primary production (NPP; N = 165) and net community production (NCP; N = 95), were used to evaluate the performance of Moderate Resolution Imaging Spectroradiometer on Aqua (MODIS-A) algorithms for these parameters, in the South Atlantic Ocean, to facilitate the accurate generation of satellite NCP time series. For Chl a, five algorithms were tested using MODIS-A data, and OC3-CI performed best, which was subsequently used to compute NPP. Of three NPP algorithms tested, a Wavelength Resolved Model (WRM) was the most accurate, and was therefore used to estimate NCP with an empirical relationship between NCP with NPP and sea surface temperature (SST). A perturbation analysis was deployed to quantify the range of uncertainties introduced in satellite NCP from input parameters. The largest reductions in the uncertainty of satellite NCP came from MODIS-A derived NPP using the WRM (40%) and MODIS-A Chl a using OC3-CI (22%). The most accurate NCP algorithm, was used to generate a 16 year time series (2002 to 2018) from MODIS-A to assess climate and environmental drivers of NCP across the South Atlantic basin. Positive correlations between wind speed anomalies and NCP anomalies were observed in the central South Atlantic Gyre (SATL), and the Benguela Upwelling (BENG), indicating that autotrophic conditions may be fuelled by local wind-induced nutrient inputs to the mixed layer. Sea Level Height Anomalies (SLHA), used as an indicator of mesoscale eddies, were negatively correlated with NCP anomalies offshore of the BENG upwelling fronts into the SATL, suggesting autotrophic conditions are driven by mesoscale features. The Agulhas bank and Brazil-Malvinas confluence regions also had a strong negative correlation between SLHA and NCP anomalies, similarly indicating that NCP is forced by mesoscale eddy generation in this region. Positive correlations between SST anomalies and the Multivariate ENSO Index (MEI) in the SATL, indicated the influence of El Niño events on the South Atlantic Ocean, however the plankton community response was less clear. UK Natural Environment Research Council | Ref. NERC; NE / L002434 / 1 European Space Agency | Ref. AMT4SentinelFRM (ESRIN / RFQ / 3-14457 / 16 / I-BG) European Space Agency | Ref. AMT4OceanSatFlux (4000125730/18 / NL / FF / gp) NERC International Opportunity Fund Grant Satellite estimates of marine net community production in the South Atlantic from Sentinel-3 | Ref. SemSAS; NE / P00878X / 1 P&D ANP / BRASOIL | Ref. 48610.011013 / 2014-66 Oceanographic Institute of the University of São Paulo | Ref. FAPESP 2015 / 01373-0 Oceanographic Institute of the University of São Paulo | Ref. CNPq 442926 / 2015-4 Oceanographic Institute of the University of São Paulo | Ref. FAPESP 2014 / 50820-7 Oceanographic Institute of the University of São Paulo | Ref. CNPq 565060 / 2010-4 NERC | Ref. NE / R015953 / 1

Results from a 1D setup of the European Regional Seas Ecosystem Model (ERSEM) biogeochemical model were compared with new observations collected under the UK Shelf Seas Biogeochemistry (SSB) programme to assess model performance and clarify elements of shelf-sea benthic biogeochemistry and carbon cycling. Observations from two contrasting sites (muddy and sandy) in the Celtic Sea in otherwise comparable hydrographic conditions were considered, with the focus on the benthic system. A standard model parameterisation with site-specific light and nutrient adjustments was used, along with modifications to the within-seabed diffusivity to accommodate the modelling of permeable (sandy) sediments. Differences between modelled and observed quantities of organic carbon in the bed were interpreted to suggest that a large part (>90%) of the observed benthic organic carbon is biologically relatively inactive. Evidence on the rate at which this inactive fraction is produced will constitute important information to quantify offshore carbon sequestration. Total oxygen uptake and oxic layer depths were within the range of the measured values. Modelled depth average pore water concentrations of ammonium, phosphate and silicate were typically 5–20% of observed values at the muddy site due to an underestimate of concentrations associated with the deeper sediment layers. Model agreement for these nutrients was better at the sandy site, which had lower pore water concentrations, especially deeper in the sediment. Comparison of pore water nitrate with observations had added uncertainty, as the results from process studies at the sites indicated the dominance of the anammox pathway for nitrogen removal; a pathway that is not included in the model. Macrofaunal biomasses were overestimated, although a model run with increased macrofaunal background mortality rates decreased macrofaunal biomass and improved agreement with observations. The decrease in macrofaunal biomass was compensated by an increase in meiofaunal biomass such that total oxygen demand remained within the observed range. The permeable sediment modification reproduced some of the observed behaviour of oxygen penetration depth at the sandy site. It is suggested that future development in ERSEM benthic modelling should focus on: (1) mixing and degradation rates of benthic organic matter, (2) validation of benthic faunal biomass against large scale spatial datasets, (3) incorporation of anammox in the benthic nitrogen cycle, and (4) further developments to represent permeable sediment processes. Electronic supplementary material The online version of this article (doi:10.1007/s10533-017-0367-0) contains supplementary material, which is available to authorized users.

We undertook a seasonal study of benthic N-cycling on the Celtic Sea continental shelf in 2015, augmented by an earlier cruise in 2014. Two cruises in 2015 were centred before and after the Spring phytoplankton bloom and a further cruise was carried out in late summer. Five sites covering the mud to sand continuum were visited on all cruises, where we determined ammonium-oxidation, anammox and denitrification rates, expression of anammox and denitrification genes, N-nutrient fluxes and sediment porewater profiles of N-nutrients. Highest process rates were found during the post-bloom and late summer periods. The Celtic Sea was overwhelmingly a source of inorganic-N to the overlying water column. The efflux of nitrate was controlled by the magnitude of ammonium-oxidation. The latter accounted for 10–16% of total Oxygen consumption in cohesive sediments and 35–56% in sandy sediments. Ammonium oxidation rates in the range of 0.001–2.288 mmol m−2 days−1 were inversely correlated with sediment porosity and positively correlated with organic matter content (OM) which together explained 66% of the variance in rates. N-removal was dominated by anammox (0.003–0.636 mmol m−2 days−1), rather than denitrification (0.000–0.034 mmol m−2 days−1). This finding was supported by the corresponding gene expression data. The expression of hydrazine oxidoreductase (anammox) was significantly correlated with anammox and total N-removal rates. Anammox was positively correlated with porosity and OM, whilst denitrification was correlated with OM. The N-requirement of these processes was largely met through nitrification (ammonium-oxidation) rather than influx from the overlying water column. We estimated that N-removal via denitrification and anammox removed 6–9% of the organic-N deposited at the sea-floor from the overlying water column. The Celtic Sea system was thereby losing N which must be replenished on an annual basis in order to sustain productivity.

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 transport of dissolved organic matter (DOM) across the land-ocean-aquatic-continuum (LOAC), from freshwater to the ocean, is an important yet poorly understood component of the global carbon budget. Exploring and quantifying this flux is a significant challenge given the complexities of DOM cycling across these contrasting environments. We developed a new model, UniDOM, that unifies concepts, state variables and parameterisations of DOM turnover across the LOAC. Terrigenous DOM is divided into two pools, T1 (strongly-UV-absorbing) and T2 (non- or weakly-UV-absorbing), that exhibit contrasting responses to microbial consumption, photooxidation and flocculation. Data are presented to show that these pools are amenable to routine measurement based on specific UV absorbance (SUVA). In addition, an autochtonous DOM pool is defined to account for aquatic DOM production. A novel aspect of UniDOM is that rates of photooxidation and microbial turnover are parameterised as an inverse function of DOM age. Model results, which indicate that ~ 5% of the DOM originating in streams may penetrate into the open ocean, are sensitive to this parameterisation, as well as rates assigned to turnover of freshly-produced DOM. The predicted contribution of flocculation to DOM turnover is remarkably low, although a mechanistic representation of this process in UniDOM was considered unachievable because of the complexities involved. Our work highlights the need for ongoing research into the mechanistic understanding and rates of photooxidation, microbial consumption and flocculation of DOM across the different environments of the LOAC, along with the development of models based on unified concepts and parameterisations.

The Surface Ocean CO2 Atlas (SOCAT) is a synthesis of quality-controlled fCO2 (fugacity of carbon dioxide) values for the global surface oceans and coastal seas with regular updates. Version 3 of SOCAT has 14.7 million fCO2 values from 3646 data sets covering the years 1957 to 2014. This latest version has an additional 4.6 million fCO2 values relative to version 2 and extends the record from 2011 to 2014. Version 3 also significantly increases the data availability for 2005 to 2013. SOCAT has an average of approximately 1.2 million surface water fCO2 values per year for the years 2006 to 2012. Quality and documentation of the data has improved. A new feature is the data set quality control (QC) flag of E for data from alternative sensors and platforms. The accuracy of surface water fCO2 has been defined for all data set QC flags. Automated range checking has been carried out for all data sets during their upload into SOCAT. The upgrade of the interactive Data Set Viewer (previously known as the Cruise Data Viewer) allows better interrogation of the SOCAT data collection and rapid creation of high-quality figures for scientific presentations. Automated data upload has been launched for version 4 and will enable more frequent SOCAT releases in the future. High-profile scientific applications of SOCAT include quantification of the ocean sink for atmospheric carbon dioxide and its long-term variation, detection of ocean acidification, as well as evaluation of coupled-climate and ocean-only biogeochemical models. Users of SOCAT data products are urged to acknowledge the contribution of data providers, as stated in the SOCAT Fair Data Use Statement. This ESSD (Earth System Science Data) "living data" publication documents the methods and data sets used for the assembly of this new version of the SOCAT data collection and compares these with those used for earlier versions of the data collection (Pfeil et al., 2013; Sabine et al., 2013; Bakker et al., 2014). Individual data set files, included in the synthesis product, can be downloaded here: doi:10.1594/PANGAEA.849770. The gridded products are available here: doi:10.3334/CDIAC/OTG.SOCAT_V3_GRID.

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.

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.

Ocean acidification, the result of increased dissolution of carbon dioxide (CO2) in seawater, is a leading subject of current research. The effects of acidification on non-calcifying macroalgae are, however, still unclear. The current study reports two 1-month studies using two different macroalgae, the red alga Palmaria palmata (Rhodophyta) and the kelp Saccharina latissima (Phaeophyta), exposed to control (pHNBS = ∼8.04) and increased (pHNBS = ∼7.82) levels of CO2-induced seawater acidification. The impacts of both increased acidification and time of exposure on net primary production (NPP), respiration (R), dimethylsulphoniopropionate (DMSP) concentrations, and algal growth have been assessed. In P. palmata, although NPP significantly increased during the testing period, it significantly decreased with acidification, whereas R showed a significant decrease with acidification only. S. latissima significantly increased NPP with acidification but not with time, and significantly increased R with both acidification and time, suggesting a concomitant increase in gross primary production. The DMSP concentrations of both species remained unchanged by either acidification or through time during the experimental period. In contrast, algal growth differed markedly between the two experiments, in that P. palmata showed very little growth throughout the experiment, while S. latissima showed substantial growth during the course of the study, with the latter showing a significant difference between the acidified and control treatments. These two experiments suggest that the study species used here were resistant to a short-term exposure to ocean acidification, with some of the differences seen between species possibly linked to different nutrient concentrations between the experiments.

The Atlantic Meridional Transect (AMT) series of twenty-five cruises over the past twenty years has produced a rich depth-resolved biogeochemical in situ data resource consisting of a wealth of core variables. These multiple core datasets, key to the operation of AMT, such as temperature, salinity, oxygen and inorganic nutrients, are often only used as ancillary measurements for contextualising hypothesis-driven process studies. In this paper these core in situ variables, alongside data drawn from satellite Earth Observation (EO) and modelling, have been analysed to determine characteristic oceanic province variations encountered over the last twenty years on the AMT through the Atlantic Ocean. The EO and modelling analysis shows the variations of key environmental variables in each province, such as surface currents, the net heat flux and subsequent large scale biological responses, such as primary production. The in situ core dataset analysis allows the variation in features such as the tropical oxygen minimum zone to be quantified as well as showing clear contrasts between the provinces in nutrient stoichiometry. Such observations and relationships can be used within basin scale biogeochemical models to set realistic variation ranges.

Here we present more than 21,000 observations of carbon dioxide fugacity in air and seawater (fCO(2)) along the Atlantic Meridional Transect (AMT) programme for the period 1995-2013. Our dataset consists of 11 southbound and 2 northbound cruises in boreal autumn and spring respectively. Our paper is primarily focused on change in the surface-ocean carbonate system during southbound cruises. We used observed fCO(2) and total alkalinity (TA), derived from salinity and temperature, to estimate dissolved inorganic carbon (DIC) and pH (total scale). Using this approach, estimated pH was consistent with spectrophotometric measurements carried out on 3 of our cruises. The AMT cruises transect a range of biogeographic provinces where surface Chlorophyll-alpha spans two orders of magnitude (mesotrophic high latitudes to oligotrophic subtropical gyres). We found that surface Chlorophyll-alpha was negatively correlated with fCO(2), but that the deep chlorophyll maximum was not a controlling variable for fCO(2). Our data show clear evidence of ocean acidification across 100 degrees of latitude in the Atlantic Ocean. Over the period 1995-2013 we estimated annual rates of change in: (a) sea surface temperature of 0.01 +/- 0.05 degrees C, (b) seawater fCO(2) of 1.44 +/- 0.84 mu atm, (c) DIC of 0.87 +/- 1.02 mu mol per kg and (d) pH of -0.0013 +/- 0.0009 units. Monte Carlo simulations propagating the respective analytical uncertainties showed that the latter were < 5% of the observed trends. Seawater fCO(2) increased at the same rate as atmospheric CO2.

Pteropods are among the first responders to ocean acidification and warming, but have not yet been widely explored as carriers of marine paleoenvironmental signals. In order to characterize the stable isotopic composition of aragonitic pteropod shells and their variation in response to climate change parameters, such as seawater temperature, pteropod shells (Heliconoides inflatus) were collected along a latitudinal transect in the Atlantic Ocean (31° N to 38° S). Comparison of shell oxygen isotopic composition to depth changes in the calculated aragonite equilibrium oxygen isotope values implies shallow calcification depths for H. inflatus (75 m). This species is therefore a good potential proxy carrier for past variations in surface ocean properties. Furthermore, we identified pteropod shells to be excellent recorders of climate change, as carbonate ion concentration and temperature in the upper water column have dominant influences on pteropod shell carbon and oxygen isotopic composition. These results, in combination with a broad distribution and high abundance, make the pteropod species studied here, H. inflatus, a promising new proxy carrier in paleoceanography.

Oceanic oxygen minimum zones are strong sources of the potent greenhouse gas N2O but its microbial source is unclear. We characterized an exponential response in N2O production to decreasing oxygen between 1 and 30 μmol O2 l−1 within and below the oxycline using 15NO2−, a relationship that held along a 550 km offshore transect in the North Pacific. Differences in the overall magnitude of N2O production were accounted for by archaeal functional gene abundance. A one-dimensional (1D) model, parameterized with our experimentally derived exponential terms, accurately reproduces N2O profiles in the top 350 m of water column and, together with a strong 45N2O signature indicated neither canonical nor nitrifier–denitrification production while statistical modelling supported production by archaea, possibly via hybrid N2O formation. Further, with just archaeal N2O production, we could balance high-resolution estimates of sea-to-air N2O exchange. Hence, a significant source of N2O, previously described as leakage from bacterial ammonium oxidation, is better described by low-oxygen archaeal production at the oxygen minimum zone's margins., Understanding the production processes behind oceanic sources of nitrous oxide (N2O), a potent greenhouse gas, is of critical importance. Here, the authors reveal an archaeal-mediated N2O production pathway in the North Pacific, which increases exponentially with decreasing oxygen.

Continental shelf sediments are globally important for biogeochemical activity. Quantification of shelf-scale stocks and fluxes of carbon and nutrients requires the extrapolation of observations made at limited points in space and time. The procedure for selecting exemplar sites to form the basis of this up-scaling is discussed in relation to a UK-funded research programme investigating biogeochemistry in shelf seas. A three-step selection process is proposed in which (1) a target area representative of UK shelf sediment heterogeneity is selected, (2) the target area is assessed for spatial heterogeneity in sediment and habitat type, bed and water column structure and hydrodynamic forcing, and (3) study sites are selected within this target area encompassing the range of spatial heterogeneity required to address key scientific questions regarding shelf scale biogeochemistry, and minimise confounding variables. This led to the selection of four sites within the Celtic Sea that are significantly different in terms of their sediment, bed structure, and macrofaunal, meiofaunal and microbial community structures and diversity, but have minimal variations in water depth, tidal and wave magnitudes and directions, temperature and salinity. They form the basis of a research cruise programme of observation, sampling and experimentation encompassing the spring bloom cycle. Typical variation in key biogeochemical, sediment, biological and hydrodynamic parameters over a pre to post bloom period are presented, with a discussion of anthropogenic influences in the region. This methodology ensures the best likelihood of site-specific work being useful for up-scaling activities, increasing our understanding of benthic biogeochemistry at the UK-shelf scale. Electronic supplementary material The online version of this article (doi:10.1007/s10533-017-0366-1) contains supplementary material, which is available to authorized users.

The Surface Ocean CO2 Atlas (SOCAT) is a synthesis of quality-controlled fCO2 (fugacity of carbon dioxide) values for the global surface oceans and coastal seas with regular updates. Version 3 of SOCAT has 14.5 million fCO2 values from 3646 data sets covering the years 1957 to 2014. This latest version has an additional 4.4 million fCO2 values relative to version 2 and extends the record from 2011 to 2014. Version 3 also significantly increases the data availability for 2005 to 2013. SOCAT has an average of approximately 1.2 million surface water fCO2 values per year for the years 2006 to 2012. Quality and documentation of the data has improved. A new feature is the data set quality control (QC) flag of E for data from alternative sensors and platforms. The accuracy of surface water fCO2 has been defined for all data set QC flags. Automated range checking has been carried out for all data sets during their upload into SOCAT. The upgrade of the interactive Data Set Viewer (previously known as the Cruise Data Viewer) allows better interrogation of the SOCAT data collection and rapid creation of high-quality figures for scientific presentations. Automated data upload has been launched for version 4 and will enable more frequent SOCAT releases in the future. High-profile scientific applications of SOCAT include quantification of the ocean sink for atmospheric carbon dioxide and its long-term variation, detection of ocean acidification, as well as evaluation of coupled-climate and ocean-only biogeochemical models. Users of SOCAT data products are urged to acknowledge the contribution of data providers, as stated in the SOCAT Fair Data Use Statement. This ESSD (Earth System Science Data) "Living Data" publication documents the methods and data sets used for the assembly of this new version of the SOCAT data collection and compares these with those used for earlier versions of the data collection (Pfeil et al., 2013; Sabine et al., 2013; Bakker et al., 2014).

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates, consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuel combustion and cement production (EFF) are based on energy statistics and cement production data, respectively, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover-change (some including nitrogen-carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2004-2013) EFF was 8.9 ± 0.4 GtC yr-1, ELUC 0.9 ± 0.5 GtC yr-1, GATM 4.3 ± 0.1 GtC yr-1, SOCEAN 2.6 ± 0.5 GtC yr-1, and SLAND 2.9 ± 0.8 GtC yr-1. For year 2013 alone, EFF grew to 9.9 ± 0.5 GtC yr-1, 2.3% above 2012, continuing the growth trend in these emissions, ELUC was 0.9 ± 0.5 GtC yr-1, GATM was 5.4 ± 0.2 GtC yr-1, SOCEAN was 2.9 ± 0.5 GtC yr-1, and SLAND was 2.5 ± 0.9 GtC yr-1. GATM was high in 2013, reflecting a steady increase in EFF and smaller and opposite changes between SOCEAN and SLAND compared to the past decade (2004-2013). The global atmospheric CO2 concentration reached 395.31 ± 0.10 ppm averaged over 2013. We estimate that EFF will increase by 2.5% (1.3-3.5%) to 10.1 ± 0.6 GtC in 2014 (37.0 ± 2.2 GtCO2 yr-1), 65% above emissions in 1990, based on projections of world gross domestic product and recent changes in the carbon intensity of the global economy. From this projection of EFF and assumed constant ELUC for 2014, cumulative emissions of CO2 will reach about 545 ± 55 GtC (2000 ± 200 GtCO2) for 1870-2014, about 75% from EFF and 25% from ELUC. This paper documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this living data set (Le Quéré et al. 2013, 2014). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP-2014)., 0, SCOPUS: ar.j, info:eu-repo/semantics/published

48 pages, 9 figures, 10 tables.-- Proyecto Carbochange, Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates as well as consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuels and industry (EFF) are based on energy statistics and cement production data, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover change (some including nitrogen–carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2005–2014), EFF was 9.0 ± 0.5 GtC yr−1, ELUC was 0.9 ± 0.5 GtC yr−1, GATM was 4.4 ± 0.1 GtC yr−1, SOCEAN was 2.6 ± 0.5 GtC yr−1, and SLAND was 3.0 ± 0.8 GtC yr−1. For the year 2014 alone, EFF grew to 9.8 ± 0.5 GtC yr−1, 0.6 % above 2013, continuing the growth trend in these emissions, albeit at a slower rate compared to the average growth of 2.2 % yr−1 that took place during 2005–2014. Also, for 2014, ELUC was 1.1 ± 0.5 GtC yr−1, GATM was 3.9 ± 0.2 GtC yr−1, SOCEAN was 2.9 ± 0.5 GtC yr−1, and SLAND was 4.1 ± 0.9 GtC yr−1. GATM was lower in 2014 compared to the past decade (2005–2014), reflecting a larger SLAND for that year. The global atmospheric CO2 concentration reached 397.15 ± 0.10 ppm averaged over 2014. For 2015, preliminary data indicate that the growth in EFF will be near or slightly below zero, with a projection of −0.6 [range of −1.6 to +0.5] %, based on national emissions projections for China and the USA, and projections of gross domestic product corrected for recent changes in the carbon intensity of the global economy for the rest of the world. From this projection of EFF and assumed constant ELUC for 2015, cumulative emissions of CO2 will reach about 555 ± 55 GtC (2035 ± 205 GtCO2) for 1870–2015, about 75 % from EFF and 25 % from ELUC. This living data update documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this data set (Le Quéré et al., 2015, 2014, 2013). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP_2015)., NERC provided funding to C. Le Quéré, R. Moriarty, and the GCP through their International Opportunities Fund specifically to support this publication (NE/103002X/1). G. P. Peters and R. M. Andrew were supported by the Norwegian Research Council (236296). J. G. Canadell was supported by the Australian Climate Change Science Programme. S. Sitch was supported by EU FP7 for funding through projects LUC4C (GA603542). R. J. Andres was supported by US Department of Energy, Office of Science, Biological and Environmental Research (BER) programmes under US Department of Energy contract DE-AC05- 00OR22725. T. A. Boden was supported by US Department of Energy, Office of Science, Biological and Environmental Research (BER) programmes under US Department of Energy contract DE-AC05-00OR22725.J. I. House was supported by the Leverhulme foundation and the EU FP7 through project LUC4C (GA603542). P. Friedlingstein was supported by the EU FP7 for funding through projects LUC4C (GA603542) and EMBRACE (GA282672). A. Arneth was supported by the EU FP7 for funding through LUC4C (603542), and the Helmholtz foundation and its ATMO programme. D. C. E. Bakker was supported by the EU FP7 for funding through project CARBOCHANGE (284879), the UK Ocean Acidification Research Programme (NE/H017046/1; funded by the Natural Environment Research Council, the Department for Energy and Climate Change and the Department for Environment, Food and Rural Affairs). L. Barbero was supported by NOAA’s Ocean Acidification Program and acknowledges support for this work from the National Aeronautics and Space Administration (NASA) ROSES Carbon Cycle Science under NASA grant 13-CARBON13_2-0080. P. Ciais acknowledges support from the European Research Council through Synergy grant ERC-2013-SyG-610028 “IMBALANCE-P”. M. Fader was supported by the EU FP7 for funding through project LUC4C (GA603542). J. Hauck was supported by the Helmholtz Postdoc Programme (Initiative and Networking Fund of the Helmholtz Association). R. A. Feely and A. J. Sutton were supported by the Climate Observation Division, Climate Program Office, NOAA, US Department of Commerce. A. K. Jain was supported by the US National Science Foundation (NSF AGS 12-43071) the US Department of Energy, Office of Science and BER programmes (DOE DE-SC0006706) and NASA LCLUC programme (NASA NNX14AD94G). E. Kato was supported by the ERTDF (S-10) from the Ministry of Environment, Japan. K. Klein Goldewijk was supported by the Dutch NWO VENI grant no. 863.14.022. S. K. Lauvset was supported by the project “Monitoring ocean acidification in Norwegian waters” from the Norwegian Ministry of Climate and Environment. V. Kitidis was supported by the EU FP7 for funding through project CARBOCHANGE (264879). C. Koven was supported by the Director, Office of Science, Office of Biological and Environmental Research of the US Department of Energy under contract no. DE-AC02-05CH11231 as part of their Regional and Global Climate Modeling Program. P. Landschützer was supported by GEOCarbon. I. T. van der Lann-Luijkx received financial support from OCW/NWO for ICOS-NL and computing time from NWO (SH-060-13). I. D. Lima was supported by the US National Science Foundation (NSF AGS-1048827). N. Metzl was supported by Institut National des Sciences de l’Univers (INSU) and Institut Paul Emile Victor (IPEV) for OISO cruises. D. R. Munro was supported by the US National Science Foundation (NSF PLR-1341647 and NSF AOAS-0944761). J. E. M. S. Nabel was supported by the German Research Foundation’s Emmy Noether Programme (PO1751/1-1) and acknowledges Julia Pongratz and Kim Naudts for their contributions. Y. Nojiri and S. Nakaoka were supported by the Global Environment Research Account for National Institutes (1432) by the Ministry of Environment of Japan. A. Olsen appreciates support from the Norwegian Research Council (SNACS, 229752). F. F. Pérez were supported by BOCATS (CTM2013-41048-P) project co-founded by the Spanish government and the Fondo Europeo de Desarrollo Regional (FEDER). B. Pfeil was supported through the European Union’s Horizon 2020 research and innovation programme AtlantOS under grant agreement no. 633211. D. Pierrot was supported by NOAA through the Climate Observation Division of the Climate Program Office. B. Poulter was supported by the EU FP7 for funding through GEOCarbon. G. Rehder was supported by BMBF (Bundesministerium für Bildung und Forschung) through project ICOS, grant no. 01LK1224D. U. Schuster was supported by NERC UKOARP (NE/H017046/1), NERC RAGANRoCC (NE/K002473/1), the European Space Agency (ESA) OceanFlux Evolution project, and EU FP7 CARBOCHANGE (264879). T. Steinhoff was supported by ICOS-D (BMBF FK 01LK1101C) and EU FP7 for funding through project CARBOCHANGE (264879). J. Schwinger was supported by the Research Council of Norway through project EVA (229771). T. Takahashi was supported by grants from NOAA and the Comer Education and Science Foundation. B. Tilbrook was supported by the Australian Department of Environment and the Integrated Marine Observing System. B. D. Stocker was supported by the Swiss National Science Foundation and FP7 funding through project EMBRACE (282672). S. van Heuven was supported by the EU FP7 for funding through project CARBOCHANGE (264879). G. R. van der Werf was supported by the European Research Council (280061). A. Wiltshire was supported by the Joint UK DECC/Defra Met Office Hadley Centre Climate Programme (GA01101) and EU FP7 Funding through project LUC4C (603542). S. Zaehle was supported by the European Research Council (ERC) under the Eu ropean Union’s Horizon 2020 research and innovation programme (QUINCY; grant agreement no. 647204). ISAM (PI: Atul K. Jain) simulations were carried out at the National Energy Research Scientific Computing Center (NERSC), which is supported by the US DOE under contract DE-AC02-05CH11231. Contributions from the Scripps Institution of Oceanography were supported under DoE grant DE-SC0012167 and by Schmidt Philanthropies. This is NOAA-PMEL contribution number 4400

22 páginas, 9 figuras, 10 tablas.-- D. C. E. Bakker ... et al.-- This work is distributed under the Creative Commons Attribution 3.0 License.-- Proyecto Carbochange, The Surface Ocean CO2 Atlas (SOCAT), an activity of the international marine carbon research community, provides access to synthesis and gridded fCO2 (fugacity of carbon dioxide) products for the surface oceans. Version 2 of SOCAT is an update of the previous release (version 1) with more data (increased from 6.3 million to 10.1 million surface water fCO2 values) and extended data coverage (from 1968–2007 to 1968–2011). The quality control criteria, while identical in both versions, have been applied more strictly in version 2 than in version 1. The SOCAT website (http://www.socat.info/) has links to quality control comments, metadata, individual data set files, and synthesis and gridded data products. Interactive online tools allow visitors to explore the richness of the data. Applications of SOCAT include process studies, quantification of the ocean carbon sink and its spatial, seasonal, year-to-year and longerterm variation, as well as initialisation or validation of ocean carbon models and coupled climate-carbon models, Support for SOCAT has been received from the University of East Anglia (UK), the Bjerknes Centre for Climate Research, the Geophysical Institute at the University of Bergen (Norway), the Climate Observation Division of the Climate Program Office of the US National Oceanic and Atmospheric Administration, the University of Washington, Oak Ridge National Laboratory (USA), PANGAEA ® Data Publisher for Earth and Environmental Data (Germany), the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (Germany), the National Institute for Environmental Studies (Japan), the Korean Institute of Ocean Science and Technology, the European Union projects CarboChange (FP7 264879) and GEO- CARBON (FP7 283080), the UK Ocean Acidification Research Programme (NE/H017046/1; funded by the Natural Environment Research Council, the Department for Energy and Climate Change and the Department for Environment, Food and Rural Affairs), the Research Council of Norway (CARBON-HEAT), the Scientific Committee on Oceanic Research (SCOR, US, OCE-0938349), the US National Science Foundation (OCE-1068958), Swedish Research Council projects (2009–2994; 2008–6228; 2009–2994) and the Swedish National Space Board (RESCUE project; REmote Sensing ocean Carbon UptakE).

The Mauritanian upwelling system is one of the most biologically productive regions of the world's oceans. Coastal upwelling transfers nutrients to the sun-lit surface ocean, thereby stimulating phytoplankton growth. Upwelling of deep waters also supplies dissolved inorganic carbon (DIC), high levels of which lead to low calcium carbonate saturation states in surface waters, with potentially adverse effects on marine calcifiers. In this study an upwelled filament off the coast of northwest Africa was followed using drifting buoys and sulphur hexafluoride to determine how the carbonate chemistry changed over time as a result of biological, physical and chemical processes. The initial pH tot in the mixed layer of the upwelled plume was 7.94 and the saturation states of calcite and aragonite were 3.4 and 2.2, respectively. As the plume moved offshore over a period of 9days, biological uptake of DIC (37 μmolkg -1) reduced pCO 2 concentrations from 540 to 410 μatm, thereby increasing pH tot to 8.05 and calcite and aragonite saturation states to 4.0 and 2.7 respectively. The increase (25 μmolkg -1) in total alkalinity over the 9day study period can be accounted for solely by the combined effects of nitrate uptake and processes that alter salinity (i.e., evaporation and mixing with other water masses). We found no evidence of significant alkalinity accumulation as a result of exudation of organic bases by primary producers. The ongoing expansion of oxygen minimum zones through global warming will likely further reduce the CaCO 3 saturation of upwelled waters, amplifying any adverse consequences of ocean acidification on the ecosystem of the Mauritanian upwelling system. © 2012. American Geophysical Union. All Rights Reserved.

CYCLOPS was a European Framework 5 program to further our understanding of phosphorus cycling in the Eastern Mediterranean. The core of CYCLOPS was a Lagrangian experiment in which buffered phosphoric acid was added to a < 4 x 4 km patch of water together with SF6 as the inert tracer. The patch was followed for nine days in total. Results obtained prior to the experiment showed that the system was typically ultra-oligotrophic and P-starved with DON:DOP, PON:POP and DIN:DIP all having ratios greatly in excess of 16:1 in surface waters. To our surprise, we found that although the added phosphate was rapidly taken up by the microbial biota, there was a small but significant decrease in chlorophyll a and no increase in primary production, together with an increase in heterotrophic bacterial activity, ciliate numbers and in the gut fullness and egg numbers in the zooplankton community. A microcosm experiment carried out using within-patch and out-of-patch water showed that the phytoplankton community were N and P co-limited while the bacteria and micrograzers were P-limited. Thus this system tends to N and P co-limitation of phytoplankton productivity in summer possibly caused by bioavailable DIN being converted into non-bioavailable forms of DON. On the basis of the data collected within the programme it was concluded that this behavior could be explained by three non-mutually exclusive processes described as (1) trophic by-pass in which the added phosphate gets directly to the grazing part of the predatory food chain from the heterotrophic bacteria bypassing the phytoplankton compartment phosphate, (2) trophic tunnelling in which phosphate is rapidly taken up by both phytoplankton and bacteria via rapid luxury consumption. This causes an immediate change in the phosphorus content but not the abundance of the prey organisms. The added P then ``reappears'' as responses at the predator level much more rapidly than expected, and (3) mixotrophic by-pass in which inorganic nutrients, including the added P, are taken up by mixotrophic ciliates directly, bypassing the phytoplankton. For details of the results of this study and the processes described, the readers are referred to the relevant papers within this volume. The implications of these results for nutrient cycling in the Eastern Mediterranean are discussed. In particular it is noted that the efficient and rapid grazing observed in this study might explain why the system although impacted by anthropogenic nutrient input has shown little or no measurable change in microbial productivity since added nutrients are rapidly transferred out of the photic zone via the by-pass and tunnelling processes and are exported from the basin. It is also suggested that fish productivity is higher than has been suggested by conventional food chain models due to this grazing. Two possible reasons for the unusual P-starved nature of the basin are presented. (c) 2005 Elsevier Ltd. All rights reserved.

Shelf sediments play a vital role in global biogeochemical cycling and are particularly important areas of oxygen consumption and carbon mineralisation. Total benthic oxygen uptake, the sum of diffusive and faunal mediated uptake, is a robust proxy to quantify carbon mineralisation. However, oxygen uptake rates are dynamic, due to the diagenetic processes within the sediment, and can be spatially and temporally variable. Four benthic sites in the Celtic Sea, encompassing gradients of cohesive to permeable sediments, were sampled over four cruises to capture seasonal and spatial changes in oxygen dynamics. Total oxygen uptake (TOU) rates were measured through a suite of incubation experiments and oxygen microelectrode profiles were taken across all four benthic sites to provide the oxygen penetration depth and diffusive oxygen uptake (DOU) rates. The difference between TOU and DOU allowed for quantification of the fauna mediated oxygen uptake and diffusive uptake. High resolution measurements showed clear seasonal and spatial trends, with higher oxygen uptake rates measured in cohesive sediments compared to the permeable sediment. The significant differences in oxygen dynamics between the sediment types were consistent between seasons, with increasing oxygen consumption during and after the phytoplankton bloom. Carbon mineralisation in shelf sediments is strongly influenced by sediment type and seasonality. Electronic supplementary material The online version of this article (doi:10.1007/s10533-017-0326-9) contains supplementary material, which is available to authorized users.