Global sea-to-air flux climatology for bromoform, dibromomethane and methyl iodide

Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I). The input of marine halogens to the stratosphere has been estimated from observations and modelling studies using low-resolution oceanic emission scenarios derived from top-down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt (Halocarbons in the Ocean and Atmosphere) database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1 degrees x 1 degrees grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global sea-to-air concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr(-1) for CHBr3, 0.78/0.98 Gmol Br yr(-1) for CH2Br2 and 1.24/1.45 Gmol Br yr(-1) for CH3I (robust fit/ordinary least squares regression techniques). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our flux calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An under-representation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom-up emission estimate and top-down approaches.

Sedimentation of acantharian cysts in the Iceland Basin: Strontium as a ballast for deep ocean particle flux, and implications for acantharian reproductive strategies

Acantharian cysts were discovered in sediment trap samples from spring 2007 at 2000 m in the Iceland Basin. Although these single-celled organisms contribute to particulate organic matter flux in the upper mesopelagic, their contribution to bathypelagic particle flux has previously been found negligible. Four time-series sediment traps were deployed and all collected acantharian cysts, which are reproductive structures. Across all traps, cysts contributed on average 3-22%, and 4―24% of particulate organic carbon and nitrogen (POC and PON) flux, respectively, during three separate collection intervals (the maximum contribution in any one trap was 48% for POC and 59% for PON). Strontium (Sr) flux during these 6 weeks reached 3 mg m―2 d―1. The acantharian celestite (SrSO4) skeleton clearly does not always dissolve in the mesopelagic as often thought, and their cysts can contribute significantly to particle flux at bathypelagic depths during specific flux events. Their large size (∼ I mm) and mineral ballast result in a sinking rate of ∼ 500 m d―1; hence, they reach the bathypelagic before dissolving. Our findings are consistent with a vertical profile of salinity-normalized Sr concentration in the Iceland Basin, which shows a maximum at 1700 m. Profiles of salinity-normalized Sr concentration in the subarctic Pacific reach maxima at ≤ 1500 m, suggesting that Acantharia might contribute to the bathypelagic particle flux there as well. We hypothesize that Acantharia at high latitudes use rapid, deep sedimentation of reproductive cysts during phytoplankton blooms so that juveniles can exploit the large quantity of organic matter that sinks rapidly to the deep sea following a bloom.

Variability in phytoplankton community structure in response to the North Atlantic Oscillation and implications for organic carbon flux

The North Atlantic Oscillation (NAO) is a major mode of variability in the North Atlantic, dominating atmospheric and oceanic conditions. Here, we examine the phytoplankton community-structure response to the NAO using the Continuous Plankton Recorder data set. In the Northeast Atlantic, in the transition region between the gyres, variability in the relative influence of subpolar or subtropical-like conditions is reflected in the physical environment. During positive NAO periods, the region experiences subpolar-like conditions, with strong wind stress and deep mixed layers. In contrast, during negative NAO periods, the region shifts toward more subtropical-like conditions. Diatoms dominate the phytoplankton community in positive NAO periods, whereas in negative NAO periods, dinoflagellates outcompete diatoms. The implications for interannual variability in deep ocean carbon flux are examined using data from the Porcupine Abyssal Plain time-series station. Contrary to expectations, carbon flux to 3000 m is enhanced when diatoms are outcompeted by other phytoplankton functional types. Additionally, highest carbon fluxes were not associated with an increase in biomineral content, which implies that ballasting is not playing a dominant role in controlling the flux of material to the deep ocean in this region. In transition zones between gyre systems, phytoplankton populations can change in response to forcing induced by opposing NAO phases.

Monitoring of a quasi-stationary eddy in the Bay of Biscay by means of satellite, in situ and model results

The presence of a quasi-stationary anticyclonic eddy within the southeastern Bay of Biscay (centred around 44°30′N-4°W) has been reported on various occasions in the bibliography. The analysis made in this study for the period 2003–2010, by using in situ and remote sensing measurements and model results shows that this mesoscale coherent structure is present almost every year from the end of winter-beginning of spring, to the beginning of fall. During this period it remains in an area limited to the east by the Landes Plateau, to the west by Le Danois Bank and Torrelavega canyon and to the northwest by the Jovellanos seamount. All the observations and analysis made in this contribution, suggest that this structure is generated between Capbreton and Torrelavega canyons. Detailed monitoring from in situ and remote sensing data of an anticyclonic quasi-stationary eddy, in 2008, shows the origin of this structure from a warm water current located around 43°42′N-3°30′W in mid-January. This coherent structure is monitored until August around the same area, where it has a marked influence on the Sea Level Anomaly, Sea Surface Temperature and surface Chlorophyll-a concentration. An eddy tracking method, applied to the outputs of a numerical model, shows that the model is able to reproduce this type of eddy, with similar 2D characteristics and lifetimes to that suggested by the observations and previous works. This is the case, for instance, of the simulated MAY04 eddy, which was generated in May 2004 around Torrelavega canyon and remained quasi-stationary in the area for 4 months. The diameter of this eddy ranged from 40 to 60 km, its azimuthal velocity was less than 20 cm s−1, its vertical extension reached 3000–3500 m depth during April and May and it was observed to interact with other coherent structures.

Air/sea DMS gas transfer in the North Atlantic: evidence for limited interfacial gas exchange at high wind speed

Shipboard measurements of eddy covariance dimethylsulfide (DMS) air–sea fluxes and seawater concentration were carried out in the North Atlantic bloom region in June/July 2011. Gas transfer coefficients (k660) show a linear dependence on mean horizontal wind speed at wind speeds up to 11 m s−1. At higher wind speeds the relationship between k660 and wind speed weakens. At high winds, measured DMS fluxes were lower than predicted based on the linear relationship between wind speed and interfacial stress extrapolated from low to intermediate wind speeds. In contrast, the transfer coefficient for sensible heat did not exhibit this effect. The apparent suppression of air–sea gas flux at higher wind speeds appears to be related to sea state, as determined from shipboard wave measurements. These observations are consistent with the idea that long waves suppress near-surface water-side turbulence, and decrease interfacial gas transfer. This effect may be more easily observed for DMS than for less soluble gases, such as CO2, because the air–sea exchange of DMS is controlled by interfacial rather than bubble-mediated gas transfer under high wind speed conditions.

The origin of sub-surface source waters define the sea-air flux of methane in the Mauritanian Upwelling, NW Africa

Concentrations and flux densities of methane were determined during a lagrangian study of an advective filament in the permanent upwelling region off western Mauritania. Newly upwelled waters were dominated by the presence of North Atlantic Central Water and surface CH4 concentrations of 2.2 ± 0.3 nmol L-1 were largely in equilibrium with atmospheric values, with surface saturations of 101.7 ± 14%. As the upwelling filament aged and was advected offshore, CH4 enriched South Atlantic Central Water from intermediate depths of 100 to 350m was entrained into the surface mixed layer of the filament following intense mixing associated with the shelf break. Surface saturations increased to 198.9 ± 15% and flux densities increased from a mean value over the shelf of 2.0 ± 1.1 µmol m-2d-1 to a maximum of 22.6 µmol m-2d-1. Annual CH4 emissions for this persistent filament were estimated at 0.77 ± 0.64 Gg which equates to a maximum of 0.35% of the global oceanic budget. This raises the known outgassing intensity of this area and highlights the importance of advecting filaments from upwelling waters as efficient vehicles for air-sea exchange.

Monitoring of a quasi-stationary eddy in the Bay of Biscay by means of satellite, in situ and model results

The presence of a quasi-stationary anticyclonic eddy within the southeastern Bay of Biscay (centred around 44°30′N-4°W) has been reported on various occasions in the bibliography. The analysis made in this study for the period 2003–2010, by using in situ and remote sensing measurements and model results shows that this mesoscale coherent structure is present almost every year from the end of winter-beginning of spring, to the beginning of fall. During this period it remains in an area limited to the east by the Landes Plateau, to the west by Le Danois Bank and Torrelavega canyon and to the northwest by the Jovellanos seamount. All the observations and analysis made in this contribution, suggest that this structure is generated between Capbreton and Torrelavega canyons. Detailed monitoring from in situ and remote sensing data of an anticyclonic quasi-stationary eddy, in 2008, shows the origin of this structure from a warm water current located around 43°42′N-3°30′W in mid-January. This coherent structure is monitored until August around the same area, where it has a marked influence on the Sea Level Anomaly, Sea Surface Temperature and surface Chlorophyll-a concentration. An eddy tracking method, applied to the outputs of a numerical model, shows that the model is able to reproduce this type of eddy, with similar 2D characteristics and lifetimes to that suggested by the observations and previous works. This is the case, for instance, of the simulated MAY04 eddy, which was generated in May 2004 around Torrelavega canyon and remained quasi-stationary in the area for 4 months. The diameter of this eddy ranged from 40 to 60 km, its azimuthal velocity was less than 20 cm s−1, its vertical extension reached 3000–3500 m depth during April and May and it was observed to interact with other coherent structures.

Ocean Net Heat Flux Influences Seasonal to Interannual Patterns of Plankton Abundance

Changes in the net heat flux (NHF) into the ocean have profound impacts on global climate. We analyse a long-term plankton time-series and show that the NHF is a critical indicator of ecosystem dynamics. We show that phytoplankton abundance and diversity patterns are tightly bounded by the switches between negative and positive NHF over an annual cycle. Zooplankton increase before the transition to positive NHF in the spring but are constrained by the negative NHF switch in autumn. By contrast bacterial diversity is decoupled from either NHF switch, but is inversely correlated (r=-0.920) with the magnitude of the NHF. We show that the NHF is a robust mechanistic tool for predicting climate change indicators such as spring phytoplankton bloom timing and length of the growing season.

Air–sea fluxes of oxygenated volatile organic compounds across the Atlantic Ocean

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.

Dimethylsulfide gas transfer coefficients from algal blooms in the Southern Ocean

Air–sea dimethylsulfide (DMS) fluxes and bulk air–sea gradients were measured over the Southern Ocean in February–March 2012 during the Surface Ocean Aerosol Production (SOAP) study. The cruise encountered three distinct phytoplankton bloom regions, consisting of two blooms with moderate DMS levels, and a high biomass, dinoflagellate-dominated bloom with high seawater DMS levels (> 15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m/s. Bin averaging the data resulted in a linear relationship between wind speed and mean gas transfer velocity consistent with that previously observed. However, the wind-speed-binned gas transfer data distribution at all wind speeds is positively skewed. The flux and seawater DMS distributions were also positively skewed, which suggests that eddy covariance-derived gas transfer velocities are consistently influenced by additional, log-normal noise. A flux footprint analysis was conducted during a transect into the prevailing wind and through elevated DMS levels in the dinoflagellate bloom. Accounting for the temporal/spatial separation between flux and seawater concentration significantly reduces the scatter in computed transfer velocity. The SOAP gas transfer velocity data show no obvious modification of the gas transfer–wind speed relationship by biological activity or waves. This study highlights the challenges associated with eddy covariance gas transfer measurements in biologically active and heterogeneous bloom environments.

Vertical fluxes and atmospheric cycling of methanol, acetaldehyde, and acetone in a coastal environment

We present here vertical fluxes of methanol, acetaldehyde, and acetone measured directly with eddy covariance (EC) during March to July 2012 near the southwest coast of the UK. The performance of the proton-transfer reaction mass spectrometer (PTR-MS) for flux measurement is characterized, with additional considerations given to the homogeneity and stationarity assumptions required by EC. Concentrations and fluxes of these compounds vary significantly with time of day and wind direction. Higher values of acetaldehyde and acetone are usually observed in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol concentration and flux do not demonstrate clear diel variability, suggesting sources in addition to plants. We estimate air–sea exchange and photochemical rates of these compounds, which are compared to measured vertical fluxes. For acetaldehyde, the mean (1�) concentration of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction outpaces production during the day. Air-sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime concentrations of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long distance transport, respectively.

Birth, life and death of a cyclonic eddy in the Southern Ocean

The ACC is a climatically relevant frontal structure of global importance that regularly develops instabilities which grow into meanders that eventually evolve into long-lived cyclonic eddies. These eddies exhibit sustain primary productivity that can last several months fuelled by local resupply of nutrients. During April-May 2015 we conducted an intensive field experiment in the Southern Ocean (SMILES) where we sampled and tracked an ACC meander as it developed into an eddy and later vanished some 90 days later. The meander and later eddy physical characteristics were observed with a combination of high resolution hydrography, ADCP and turbulence observations in addition to surface and depth resolved biogeochemical observations of nutrients and phytoplankton. The life and death of the eddy was subsequently tracked through ARGO, BIO-ARGO and remote sensing.