Low colloidal associations of aluminium and titanium in surface waters of the tropical Atlantic

The distribution of dissolved, soluble and colloidal fractions of Al and Ti was assessed by ultrafiltration studies in the upper water column of the eastern tropical North Atlantic. The dissolved fractions of both metals were found to be dominated by the soluble phase smaller than 10 kDa. The colloidal associations were very low (0.2–3.4%) for Al and not detectable for Ti. These findings are in some contrast to previous estimations for Ti and to the predominant occurrence of both metals as hydrolyzed species in seawater. However, low tendencies to form inorganic colloids can be expected, as in seawater dissolved Al and dissolved Ti are present within their inorganic solubility levels. In addition, association with functional organic groups in the colloidal phase is unlikely for both metals. Vertical distributions of the dissolved fractions showed surface maxima with up to 43 nM of Al and 157 pM of Ti, reflecting their predominant supply from atmospheric sources to the open ocean. In the surface waters, excess dissolved Al over dissolved Ti was present compared to the crustal source, indicating higher solubility and thus elevated inputs of dissolved Al from atmospheric mineral particles. At most stations, subsurface minima of Al and Ti were observed and can be ascribed to scavenging processes and/or biological uptake. The dissolved Al concentrations decreased by 80–90% from the surface maximum to the subsurface minimum. Estimated residence times in the upper 100 m of the water column ranged between 1.6 and 4 years for dissolved Al and between 14 and 17 years for dissolved Ti. The short residence times are in some contrast to the low colloidal associations of Al and Ti and the assumed role of colloids as intermediates in scavenging processes. This suggests that either the removal of both metals occurs predominantly via direct transfer of the hydrolyzed species into the particulate fraction or that the colloidal phase is rapidly turned over in the upper water column.

Coccolithophore surface distributions in the North Atlantic and their modulation of the air-sea flux of CO2 from 10 years of satellite Earth observation data

Coccolithophores are the primary oceanic phytoplankton responsible for the production of calcium carbonate (CaCO3). These climatically important plankton play a key role in the oceanic carbon cycle as a major contributor of carbon to the open ocean carbonate pump (similar to 50 %) and their calcification can affect the atmosphere-to-ocean (air-sea) uptake of carbon dioxide (CO2) through increasing the seawater partial pressure of CO2 (pCO(2)). Here we document variations in the areal extent of surface blooms of the globally important coccolithophore, Emiliania huxleyi, in the North Atlantic over a 10-year period (1998-2007), using Earth observation data from the Sea-viewing Wide Field-of-view Sensor (SeaWiFS). We calculate the annual mean sea surface areal coverage of E. huxleyi in the North Atlantic to be 474 000 +/- 104 000 km(2), which results in a net CaCO3 carbon (CaCO3-C) production of 0.14-1.71 Tg CaCO3-C per year. However, this surface coverage (and, thus, net production) can fluctuate inter-annually by -54/+81% about the mean value and is strongly correlated with the El Nino/Southern Oscillation (ENSO) climate oscillation index (r = 0.75, p < 0.02). Our analysis evaluates the spatial extent over which the E. huxleyi blooms in the North Atlantic can increase the pCO(2) and, thus, decrease the localised air-sea flux of atmospheric CO2. In regions where the blooms are prevalent, the average reduction in the monthly air-sea CO2 flux can reach 55%. The maximum reduction of the monthly air-sea CO2 flux in the time series is 155 %. This work suggests that the high variability, frequency and distribution of these calcifying plankton and their impact on pCO(2) should be considered if we are to fully understand the variability of the North Atlantic air-to-sea flux of CO2. We estimate that these blooms can reduce the annual N. Atlantic net sink atmospheric CO2 by between 3-28 %.

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.

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.

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.

Exploiting satellite earth observation to quantify current global oceanic DMS flux and its future climate sensitivity

We used coincident Envisat RA2 and AATSR temperature and wind speed data from 2008/2009 to calculate the global net sea-air flux of dimethyl sulfide (DMS), which we estimate to be 19.6 Tg S a21. Our monthly flux calculations are compared to open ocean eddy correlation measurements of DMS flux from 10 recent cruises, with a root mean square difference of 3.1 lmol m22 day21. In a sensitivity analysis, we varied temperature, salinity, surface wind speed, and aqueous DMS concentration, using fixed global changes as well as CMIP5 model output. The range of DMS flux in future climate scenarios is discussed. The CMIP5 model predicts a reduction in surface wind speed and we estimate that this will decrease the global annual sea-air flux of DMS by 22% over 25 years. Concurrent changes in temperature, salinity, and DMS concentration increase the global flux by much smaller amounts. The net effect of all CMIP5 modelled 25 year predictions was a 19% reduction in global DMS flux. 25 year DMS concentration changes had significant regional effects, some positive (Southern Ocean, North Atlantic, Northwest Pacific) and some negative (isolated regions along the Equator and in the Indian Ocean). Using satellite-detected coverage of coccolithophore blooms, our estimate of their contribution to North Atlantic DMS emissions suggests that the coccolithophores contribute only a small percentage of the North Atlantic annual flux estimate, but may be more important in the summertime and in the northeast Atlantic.