ALBERT

Description: Here we make an initial step toward the development of an ocean assimilation system that can constrain the modelled Atlantic Meridional Overturning Circulation (AMOC) to support climate predictions. A detailed comparison is presented of 1° and 1/4° resolution global model simulations with and without sequential data assimilation, to the observations and transport estimates from the RAPID mooring array across 26.5° N in the Atlantic. Comparisons of modelled water properties with the observations from the merged RAPID boundary arrays demonstrate the ability of in situ data assimilation to accurately constrain the east-west density gradient between these mooring arrays. However, the presence of an unconstrained "western boundary wedge" between Abaco Island and the RAPID mooring site WB2 (16 km offshore) leads to the intensification of an erroneous southwards flow in this region when in situ data are assimilated. The result is an overly intense southward upper mid-ocean transport (0–1100 m) as compared to the estimates derived from the RAPID array. Correction of upper layer zonal density gradients is found to compensate mostly for a weak subtropical gyre circulation in the free model run (i.e. with no assimilation). Despite the important changes to the density structure and transports in the upper layer imposed by the assimilation, very little change is found in the amplitude and sub-seasonal variability of the AMOC. This shows that assimilation of upper layer density information projects mainly on the gyre circulation with little effect on the AMOC at 26° N due to the absence of corrections to density gradients below 2000 m (the maximum depth of Argo). The sensitivity to initial conditions was explored through two additional experiments using a climatological initial condition. These experiments showed that the weak bias in gyre intensity in the control simulation (without data assimilation) develops over a period of about 6 months, but does so independently from the overturning, with no change to the AMOC. However, differences in the properties and volume transport of North Atlantic Deep Water (NADW) persisted throughout the 3 year simulations resulting in a difference of 3 Sv in AMOC intensity. The persistence of these dense water anomalies and their influence on the AMOC is promising for the development of decadal forecasting capabilities. The results suggest that the deeper waters must be accurately reproduced in order to constrain the AMOC.

Description: Since April 2004 the RAPID array has made continuous measurements of the Atlantic Meridional Overturning Circulation (AMOC) at 26° N. Two key components of this system are Ekman transport zonally integrated across 26° N and western boundary current transport in the Florida Straits. Whilst measurements of the AMOC as a whole are somewhat in their infancy, this study investigates what useful information can be extracted on the variability of the Ekman and Florida Straits transports using the decadal timeseries already available. Analysis is also presented for Sverdrup transports zonally integrated across 26° N. The seasonal cycles of Florida Straits, Ekman and Sverdrup transports are quantified at 26° N using harmonic analysis of annual and semi-annual constituents. Whilst Sverdrup transport shows clear semi-annual periodicity, calculations of seasonal Florida Straits and Ekman transports show substantial interannual variability due to contamination by variability at non-seasonal frequencies; the mean seasonal cycle for these transports only emerges from decadal length observations. The Florida Straits and Ekman mean seasonal cycles project on the AMOC with a combined peak-to-peak seasonal range of 3.5 Sv. The combined seasonal range for heat transport is 0.40 PW. The Florida Straits seasonal cycle possesses a smooth annual periodicity in contrast with previous studies suggesting a more asymmetric structure. No clear evidence is found to support significant changes in the Florida Straits seasonal cycle at sub-decadal periods. Whilst evidence of wind driven Florida Straits transport variability is seen at sub-seasonal and annual periods, a model run from the 1/4° eddy-permitting ocean model NEMO is used to identify an important contribution from internal oceanic variability at sub-annual and interannual periods. The Ekman transport seasonal cycle possesses less symmetric structure, due in part to different seasonal transport regimes east and west of 50 to 60° W. Around 60% of non-seasonal Ekman transport variability occurs in phase section-wide at 26° N and is related to the NAO, whilst Sverdrup transport variability is more difficult to decompose.

Description: The rugged submarine topography of the Azores supports a diverse heterozoan association resulting in intense biotically-controlled carbonate-production and accumulation. In order to characterise this cold-water (C) factory a 2-year experiment was carried out in the southern Faial Channel to study the biodiversity of hardground communities and for budgeting carbonate production and degradation along a bathymetrical transect from the intertidal to bathyal 500 m depth. Seasonal temperatures peak in September (above a thermocline) and bottom in March (stratification diminishes) with a decrease in amplitude and absolute values with depth, and tidal-driven short-term fluctuations. Measured seawater stable isotope ratios and levels of dissolved nutrients decrease with depth, as do the calcium carbonate saturation states. The photosynthetic active radiation shows a base of the euphotic zone in ~70 m and a dysphotic limit in ~150 m depth. Bioerosion, being primarily a function of light availability for phototrophic endoliths and grazers feeding upon them, is ~10 times stronger on the illuminated upside versus the shaded underside of substrates in the photic zone, with maximum rates in the intertidal (−631 g/m2/yr). Rates rapidly decline towards deeper waters where bioerosion and carbonate accretion are slow and epibenthic/endolithic communities take years to mature. Accretion rates are highest in the lower euphotic zone (955 g/m2/yr), where the substrate is less prone to hydrodynamic force. Highest rates are found – inversely to bioerosion – on down-facing substrates, suggesting that bioerosion may be a key factor governing the preferential settlement and growth of calcareous epilithobionts on down-facing substrates. In context of a latitudinal gradient, the Azores carbonate cycling rates plot between known values from the cold-temperate Swedish Kosterfjord and the tropical Bahamas, with a total range of two orders in magnitude. Carbonate budget calculations for the bathymetrical transect yield a mean 266.9 kg of epilithic carbonate production, −54.6 kg of bioerosion, and 212.3 kg of annual net carbonate production per metre of coastline in the Azores C factory.

Description: A simple prognostic tool for gas hydrate (GH) quantification in marine sediments is presented based on a diagenetic transport-reaction model approach. One of the most crucial factors for the application of diagenetic models is the accurate formulation of microbial degradation rates of particulate organic carbon (POC) and the coupled formation of biogenic methane. Wallmann et al. (2006) suggested a kinetic formulation considering the ageing effects of POC and accumulation of reaction products (CH4, CO2) in the pore water. This model is applied to data sets of several ODP sites in order to test its general validity. Based on a thorough parameter analysis considering a wide range of environmental conditions, the POC accumulation rate (POCar in g/m2/yr) and the thickness of the gas hydrate stability zone (GHSZ in m) were identified as the most important and independent controls for biogenic GH formation. Hence, depth-integrated GH inventories in marine sediments (GHI in g of CH4 per cm2 seafloor area) can be estimated as: GHI=a ·POCar·GHSZb ·exp(−GHSZc/POCar/d)+e with a = 0.00214, b = 1.234, c = −3.339, d = 0.3148, e = −10.265. The transfer function gives a realistic first order approximation of the minimum GH inventory in low gas flux (LGF) systems. The overall advantage of the presented function is its simplicity compared to the application of complex numerical models, because only two easily accessible parameters need to be determined.

Description: Iron is a key micronutrient for phytoplankton growth in the surface ocean. Yet the significance of volcanism for the marine biogeochemical iron-cycle is poorly constrained. Recent studies, however, suggest that offshore deposition of airborne ash from volcanic eruptions is a way to inject significant amounts of bio-available iron into the surface ocean. Volcanic ash may be transported up to several tens of kilometers high into the atmosphere during large-scale eruptions and fine ash may stay aloft for days to weeks, thereby reaching even the remotest and most iron-starved oceanic regions. Scientific ocean drilling demonstrates that volcanic ash layers and dispersed ash particles are frequently found in marine sediments and that therefore volcanic ash deposition and iron-injection into the oceans took place throughout much of the Earth's history. Natural evidence and the data now available from geochemical and biological experiments and satellite techniques suggest that volcanic ash is a so far underestimated source for iron in the surface ocean, possibly of similar importance as aeolian dust. Here we summarise the development of and the knowledge in this fairly young research field. The paper covers a wide range of chemical and biological issues and we make recommendations for future directions in these areas. The review paper may thus be helpful to improve our understanding of the role of volcanic ash for the marine biogeochemical iron-cycle, marine primary productivity and the ocean-atmosphere exchange of CO2 and other gases relevant for climate in the Earth's history.

Description: We review here the available information on methane (CH4) and nitrous oxide (N2O) from major marine, mostly coastal, oxygen (O2)-deficient zones formed both naturally and as a result of human activities (mainly eutrophication). Concentrations of both gases in subsurface waters are affected by ambient O2 levels to varying degrees. Organic matter supply to seafloor appears to be the primary factor controlling CH4 production in sediments and its supply to (and concentration in) overlying waters, with bottom-water O2-deficiency exerting only a modulating effect. High (micromolar level) CH4 accumulation occurs in anoxic (sulphidic) waters of silled basins, such as the Black Sea and Cariaco Basin, and over the highly productive Namibian shelf. In other regions experiencing various degrees of O2-deficiency (hypoxia to anoxia), CH4 concentrations vary from a few to hundreds of nanomolar levels. Since coastal O2-deficient zones are generally very productive and are sometimes located close to river mouths and submarine hydrocarbon seeps, it is difficult to differentiate any O2-deficiency-induced enhancement from in situ production of CH4 in the water column and its inputs through freshwater runoff or seepage from sediments. While the role of bottom-water O2-deficiency in CH4 formation appears to be secondary, even when CH4 accumulates in O2-deficient subsurface waters, methanotrophic activity severely restricts its diffusive efflux to the atmosphere. As a result, an intensification or expansion of coastal O2-deficient zones will probably not drastically change the present status where emission from the ocean as a whole forms an insignificant term in the atmospheric CH4 budget. The situation is different for N2O, the production of which is greatly enhanced in low-O2 waters, and although it is lost through denitrification in most suboxic and anoxic environments, the peripheries of such environments offer most suitable conditions for its production, with the exception of enclosed anoxic basins. Most O2-deficient systems serve as strong net sources of N2O to the atmosphere. This is especially true for coastal upwelling regions with shallow O2-deficient zones where a dramatic increase in N2O production often occurs in rapidly denitrifying waters. Nitrous oxide emissions from these zones are globally significant, and so their ongoing intensification and expansion is likely to lead to a significant increase in N2O emission from the ocean. However, a meaningful quantitative prediction of this increase is not possible at present because of continuing uncertainties concerning the formative pathways to N2O as well as insufficient data from key coastal regions.

Description: The role played by wind-forced anticyclones in the vertical transport and mixing at the ocean mesoscale is investigated with a primitive-equation numerical model in an idealized configuration. The focus of this work is to determine how the stratification impacts such transport. The flows, forced only at the surface by an idealized wind forcing, are predominantly horizontal and, on average, quasigeostrophic. Inside vortex cores and intense filaments, however, the dynamics is strongly ageostrophic. Mesoscale anticyclones appear as "islands" of increased penetration of wind energy into the ocean interior and they represent the maxima of available potential energy. The amount of available potential energy is directly correlated with the degree of stratification. The wind energy injected at the surface is transferred at depth through the generation and subsequent straining effect of Vortex Rossby Waves (VRWs), and through near-inertial internal oscillations trapped inside anticyclonic vortices. Both these mechanisms are affected by stratification. Stronger transfer but larger confinement close to the surface is found when the stratification is stronger. For weaker stratification, vertical mixing close to the surface is less intense but below about 150 m attains substantially higher values due to an increased contribution of both VRWs, whose time scale is on the order of few days, and of near-inertial motions, with a time scale of few hours.

Description: We present the first application of Stochastic Heterogeneity Mapping based on the band-limited von Kármán function to a seismic reflection stack of a Mediterranean water eddy (meddy), a large salt lens of Mediterranean water. This process extracts two stochastic parameters directly from the reflectivity field of the seismic data: the Hurst number, which ranges from 0 to 1, and the correlation length (scale length). Lower Hurst numbers represent a richer range of high wavenumbers and correspond to a broader range of heterogeneity in reflection events. The Hurst number estimate for the top of the meddy (0.39) compares well with recent theoretical work, which required values between 0.25 and 0.5 to model internal wave surfaces in open ocean conditions based on simulating a Garrett-Munk spectrum (GM76) slope of −2. The scale lengths obtained do not fit as well to seismic reflection events as those used in other studies to model internal waves. We suggest two explanations for this discrepancy: (1) due to the fact that the stochastic parameters are derived from the reflectivity field rather than the impedance field the estimated scale lengths may be underestimated, as has been reported; and (2) because the meddy seismic image is a two-dimensional slice of a complex and dynamic three-dimensional object, the derived scale lengths are biased to the direction of flow. Nonetheless, varying stochastic parameters, which correspond to different spectral slopes in the Garrett-Munk spectrum (horizontal wavenumber spectrum), can provide an estimate of different internal wave scales from seismic data alone. We hence introduce Stochastic Heterogeneity Mapping as a novel tool in physical oceanography.

Description: We study the contribution of eastern-boundary density variations to sub-seasonal and seasonal anomalies of the strength and vertical structure of the Atlantic Meridional Overturning Circulation (AMOC) at 26.5° N, by means of the RAPID/MOCHA mooring array between April 2004 and October 2007. The major density anomalies are found in the upper 500 m, and they are often coherent down to 1400 m. The densities have 13-day fluctuations that are apparent down to 3500 m. The two strategies for measuring eastern-boundary density – a tall offshore mooring (EB1) and an array of moorings on the continental slope (EBH) – show little correspondence in terms of amplitude, vertical structure, and frequency distribution of the resulting basin-wide integrated transport fluctuations, implying that there are significant transport contributions between EB1 and EBH. Contrary to the original planning, measurements from EB1 cannot serve as backup or replacement for EBH: density needs to be measured directly at the continental slope to compute the full-basin density gradient. Fluctuations in density at EBH generate transport variability of 2 Sv rms in the AMOC, while the overall AMOC variability is 4.8 Sv rms. There is a pronounced deep-reaching seasonal cycle in density at the eastern boundary, which is apparent between 100 m and 1400 m, with maximum positive anomalies in spring and maximum negative anomalies in autumn. These changes drive anomalous southward upper mid-ocean flow in spring, implying maximum reduction of the AMOC, and vice-versa in autumn. The amplitude of the seasonal cycle of the AMOC arising from the eastern-boundary densities is 5.2 Sv peak-to-peak, dominating the 6.7 Sv peak-to-peak seasonal cycle of the total AMOC. Our analysis suggests that the seasonal cycle in density may be forced by the strong near-coastal seasonal cycle in wind stress curl.

Description: Water column data of carbon and carbon-relevant hydrographic and hydrochemical parameters from 188 cruises in the Arctic Mediterranean Seas, Atlantic and Southern Ocean have been retrieved and merged in a new data base: the CARINA (CARbon IN the Atlantic) Project. These data have gone through rigorous quality control (QC) procedures so as to improve the quality and consistency of the data as much as possible. Secondary quality control, which involved objective study of data in order to quantify systematic differences in the reported values, was performed for the pertinent parameters in the CARINA data base. Systematic biases in the data have been tentatively corrected in the data products. The products are three merged data files with measured, adjusted and interpolated data of all cruises for each of the three CARINA regions (Arctic Mediterranean Seas, Atlantic and Southern Ocean). Ninety-eight cruises were conducted in the "Atlantic" defined as the region south of the Greenland-Iceland-Scotland Ridge and north of about 30° S. Here we report the details of the secondary QC which was done on the total dissolved inorganic carbon (TCO2) data and the adjustments that were applied to yield the final data product in the Atlantic. Procedures of quality control – including crossover analysis between stations and inversion analysis of all crossover data – are briefly described. Adjustments were applied to TCO2 measurements for 17 of the cruises in the Atlantic Ocean region. With these adjustments, the CARINA data base is consistent both internally as well as with GLODAP data, an oceanographic data set based on the WOCE Hydrographic Program in the 1990s, and is now suitable for accurate assessments of, for example, regional oceanic carbon inventories, uptake rates and model validation.

Description: The chemical characterization of filter high volume (HV) and Berner impactor (BI) samples PM during RHaMBLe (Reactive Halogens in the Marine Boundary Layer) 2007 shows that the Cape Verde aerosol particles are mainly composed of sea salt, mineral dust and associated water. Minor components are nss-salts, OC and EC. The influence from the African continent on the aerosol constitution was generally small but air masses which came from south-western Europe crossing the Canary Islands transported dust to the sampling site together with other loadings. The mean mass concentration was determined for PM10 to 17 μg/m3 from impactor samples and to 24.2 μg/m3 from HV filter samples. Non sea salt (nss) components of PM were found in the submicron fractions and nitrate in the coarse mode fraction. Bromide was found in all samples with much depleted concentrations in the range 1–8 ng/m3 compared to fresh sea salt aerosol indicating intense atmospheric halogen chemistry. Loss of bromide by ozone reaction during long sampling time is supposed and resulted totally in 82±12% in coarse mode impactor samples and in filter samples in 88±6% bromide deficits. A chloride deficit was determined to 8% and 1% for the coarse mode particles (3.5–10 μm; 1.2–3.5 μm) and to 21% for filter samples. During 14 May with high mineral dust loads also the maximum of OC (1.71μg/m3) and EC (1.25 μg/m3) was measured. The minimum of TC (0.25 μg/m3) was detected during the period 25 to 27 May when pure marine air masses arrived. The concentrations of carbonaceous material decrease with increasing particle size from 60% for the ultra fine particles to 2.5% in coarse mode PM. Total iron (dust vs. non-dust: 0.53 vs. 0.06 μg m3), calcium (0.22 vs. 0.03 μg m3) and potassium (0.33 vs. 0.02 μg m3) were found as good indicators for dust periods because of their heavily increased concentration in the 1.2 to 3.5 μm fraction as compared to their concentration during the non-dust periods. For the organic constituents, oxalate (78–151 ng/m3) and methanesulfonic acid (MSA, 25–100 ng/m3) are the major compounds identified. A good correlation between nss-sulphate and MSA was found for the majority of days indicating active DMS chemistry and low anthropogenic influences.

Description: The future behaviour of the global ocean as a sink for CO2 is significant for climate change, but it is also important to understand its past by quantifying anthropogenic CO2 (Cant) in the ocean today. Unfortunately, this is complicated by the difficulty of deconvoluting Cant from the natural, unperturbed carbon cycle. Nonetheless, a range of techniques have been devised that perform this separation using the information implicit in other physical, biogeochemical and artificial ocean tracers. One such method is the TrOCA approach, whose parameterisation is derived from relationships between biogeochemical tracers within watermasses defined by age tracers such as CFC-11. TrOCA has a number of methodological advantages, and has been shown to be plausible, relative to other methods, in a number of studies. Here we examine the TrOCA approach by using it to deconvolute the known distribution of Cant from an ocean general circulation model (OGCM) simulation of the industrial period (1864–2004). TrOCA is evaluated at local, regional and global scales, with an emphasis on the wider applicability of the parameterisations derived at these scales. Our work finds that the published TrOCA parameterisation performs poorly when extrapolated beyond its calibration region, either with observational data or (especially) model output. Optimising TrOCA parameters using model output as a synthetic dataset leads to some small improvements, but the resulting TrOCA variants still perform poorly. Furthermore, there are large ranges on the optimised TrOCA parameters suggesting that a "universal" TrOCA parameterisation is not achieveable.

Description: Iron is a key limiting micro-nutrient for marine primary productivity. It can be supplied to the ocean by atmospheric dust deposition. Volcanic ash deposition into the ocean represents another external and so far largely neglected source of iron. This study demonstrates strong evidence for natural fertilisation in the iron-limited oceanic area of the NE Pacific, induced by volcanic ash from the eruption of Kasatochi volcano in August 2008. Atmospheric and oceanic conditions were favourable to generate a massive phytoplankton bloom in the NE Pacific Ocean which for the first time strongly suggests a connection between oceanic iron-fertilisation and volcanic ash supply.

Description: Very short-lived halocarbons are significant sources of reactive halogen in the marine boundary layer, and likely in the upper troposphere and lower stratosphere. Quantifying ambient concentrations in the surface ocean and atmosphere is essential for understanding the atmospheric impact of these trace gas fluxes. Despite the body of literature increasing substantially over recent years, calibration issues complicate the comparison of results and limit the utility of building larger-scale databases that would enable further development of the science (e.g. sea-air flux quantification, model validation, etc.). With this in mind, thirtyone scientists from both atmospheric and oceanic halocarbon communities in eight nations gathered in London in February 2008 to discuss the scientific issues and plan an international effort toward developing common calibration scales (http://tinyurl.com/c9cg58). Here, we discuss the outputs from this meeting, suggest the compounds that should be targeted initially, identify opportunities for beginning calibration and comparison efforts, and make recommendations for ways to improve the comparability of previous and future measurements.

Description: The conversion of fixed nitrogen to N2 in suboxic waters is estimated to contribute roughly a third to total oceanic losses of fixed nitrogen and is hence understood to be of major importance to global oceanic production and, therefore, to the role of the ocean as a sink of atmospheric CO2. At present heterotrophic denitrification and autotrophic anammox are considered the dominant sinks of fixed nitrogen. Recently, it has been suggested that the trophic nature of pelagic N2-production may have additional, "collateral" effects on the carbon cycle, where heterotrophic denitrification provides a shallow source of CO2 and autotrophic anammox a shallow sink. Here, we analyse the stoichiometries of nitrogen and associated carbon conversions in marine oxygen minimum zones (OMZ) focusing on heterotrophic denitrification, autotrophic anammox, and dissimilatory nitrate reduction to nitrite and ammonium in order to test this hypothesis quantitatively. For open ocean OMZs the combined effects of these processes turn out to be clearly heterotrophic, even with high shares of the autotrophic anammox reaction in total N2-production and including various combinations of dissimilatory processes which provide the substrates to anammox. In such systems, the degree of heterotrophy (ΔCO2:ΔN2), varying between 1.7 and 6, is a function of the efficiency of nitrogen conversion. On the contrary, in systems like the Black Sea, where suboxic N-conversions are supported by diffusive fluxes of NH4+ originating from neighbouring waters with sulphate reduction, much lower values of ΔCO2:ΔN2 can be found. However, accounting for concomitant diffusive fluxes of CO2, ratios approach higher values similar to those computed for open ocean OMZs. Based on our analysis, we question the significance of collateral effects concerning the trophic nature of suboxic N-conversions on the marine carbon cycle.

Description: Recent suggestions to slow down the increase in atmospheric carbon dioxide have included ocean fertilization by addition of the micronutrient iron to Southern Ocean surface waters, where a number of natural and artificial iron fertilization experiments have shown that low ambient iron concentrations limit phytoplankton growth. Using a coupled carbon-climate model with the marine biology's response to iron addition calibrated against data from natural iron fertilization experiments, we examine biogeochemical side effects of a hypothetical large-scale Southern Ocean Iron Fertilization (OIF) that need to be considered when attempting to account for possible OIF-induced carbon offsets. In agreement with earlier studies our model simulates an OIF-induced increase in local air-sea CO2 fluxes by about 60 GtC over a 100-year period, which amounts to about 40% of the OIF-induced increase in organic carbon export. Offsetting CO2 return fluxes outside the region and after stopping the fertilization at 1, 7, 10, 50, and 100 years are quantified for a typical accounting period of 100 years. For continuous Southern Ocean iron fertilization, the return flux outside the fertilized area cancels about 8% of the fertilization-induced CO2 air-sea flux within the fertilized area on a 100-yr timescale. This "leakage" effect has a similar radiative impact as the simulated enhancement of marine N2O emissions. Other side effects not yet discussed in terms of accounting schemes include a decrease in Southern Ocean oxygen levels and a simultaneous shrinking of tropical suboxic areas, and accelerated ocean acidification in the entire water column in the Southern Ocean on the expense of reduced globally averaged surface water acidification. A prudent approach to account for the OIF-induced carbon sequestration would account for global air-sea CO2 fluxes rather than for local fluxes into the fertilized area only. However, according to our model, this would underestimate the potential for offsetting CO2 emissions by about 20% on a 100 year accounting timescale. We suggest that a fair accounting scheme applicable to both terrestrial and marine carbon sequestration has to be based on emission offsets rather than on changes in individual carbon pools.

Description: Rising atmospheric CO2 is acidifying the surface ocean, a process which is expected to greatly influence the chemistry and biology of the future ocean. Following the development of iron-replete phytoplankton blooms in a coastal mesocosm experiment at 350, 700, and 1050 μatm pCO2, we observed significant increases in dissolved iron concentrations, Fe(II) concentrations, and Fe(II) half-life times during and after the peak of blooms in response to CO2 enrichment and concomitant lowering of pH, suggesting increased iron bioavailability. If applicable to the open ocean this may provide a negative feedback mechanism to the rising atmospheric CO2 by stimulating marine primary production.

Description: The response of the coccolithophore Emiliania huxleyi to rising CO2 concentrations is well documented for acclimated cultures where cells are exposed to the CO2 treatments for several generations prior to the experiment. The exact number of generations required for acclimation to CO2-induced changes in seawater carbonate chemistry, however, is unknown. Here we show that Emiliania huxleyi's short-term response (26 h) after cultures (grown at 500 μatm) were abruptly exposed to changed CO2 concentrations (~190, 410, 800 and 1500 μatm) is similar to that obtained with acclimated cultures under comparable conditions in earlier studies. Most importantly, from the lower CO2 levels (190 and 410 μatm) to 750 and 1500 μatm calcification decreased and organic carbon fixation increased within the first 8 to 14 h after exposing the cultures to changes in carbonate chemistry. This suggests that Emiliania huxleyi rapidly alters the rates of essential metabolical processes in response to changes in seawater carbonate chemistry, establishing a new physiological "state" (acclimation) within a matter of hours. If this relatively rapid response applies to other phytoplankton species, it may simplify interpretation of studies with natural communities (e.g. mesocosm studies and ship-board incubations), where often it is not feasible to allow for a pre-conditioning phase before starting experimental incubations.

Description: The physiological performance of two coccolithophore species, Emiliania huxleyi and Coccolithus braarudii, was investigated during long-term exposure to elevated pCO2 levels. Mono-specific cultures were grown over 152 (E. huxleyi) and 65 (C. braarudii) generations while pCO2 was gradually increased to maximum levels of 1150 μatm (E. huxleyi) and 930 μatm (C. braarudii) and kept constant thereafter. Rates of cell growth and cell quotas of particulate organic carbon (POC), particulate inorganic carbon (PIC) and total particulate nitrogen (TPN) were determined repeatedly throughout the incubation period. Increasing pCO2 caused a decrease in cell growth rate of 9% and 29% in E. huxleyi and C. braarudii, respectively. In both species cellular PIC:TPN and PIC:POC ratios decreased in response to rising pCO2, whereas no change was observed in the POC:TPN ratios of E. huxleyi and C. braarudii. These results are consistent with those obtained in shorter-term high CO2 exposure experiments following abrupt pertubations of the seawater carbonate system and indicate that for the strains tested here a gradual CO2 increase does not alleviate CO2/pH sensitivity.

Description: CO2/pH perturbation experiments were carried out under two different pCO2 levels (39.3 and 101.3 Pa) to evaluate effects of CO2-induced ocean acidification on the marine diatom Phaeodactylum tricornutum. After acclimation (〉20 generations) to ambient and elevated CO2 conditions (with corresponding pH values of 8.15 and 7.80, respectively), growth and photosynthetic carbon fixation rates of high CO2 grown cells were enhanced by 5% and 12%, respectively, and dark respiration stimulated by 34% compared to cells grown at ambient CO2. The half saturation constant (Km) for carbon fixation (dissolved inorganic carbon, DIC) increased by 20% under the low pH and high CO2 condition, reflecting a decreased affinity for HCO3– or/and CO2 and down-regulated carbon concentrating mechanism (CCM). In the high CO2 grown cells, the electron transport rate from photosystem II (PSII) was photoinhibited to a greater extent at high levels of photosynthetically active radiation, while non-photochemical quenching was reduced compared to low CO2 grown cells. This was probably due to the down-regulation of CCM, which serves as a sink for excessive energy. The balance between these positive and negative effects on diatom productivity will be a key factor in determining the net effect of rising atmospheric CO2 on ocean primary production.

Description: The potential impact of rising carbon dioxide (CO2) on carbon transfer from phytoplankton to bacteria was investigated during the 2005 PeECE III mesocosm study in Bergen, Norway. Sets of mesocosms, in which a phytoplankton bloom was induced by nutrient addition, were incubated under 1× (~350 μatm), 2× (~700 μatm), and 3× present day CO2 (~1050 μatm) initial seawater and sustained atmospheric CO2 levels for 3 weeks. 13C labelled bicarbonate was added to all mesocosms to follow the transfer of carbon from dissolved inorganic carbon (DIC) into phytoplankton and subsequently heterotrophic bacteria, and settling particles. Isotope ratios of polar-lipid-derived fatty acids (PLFA) were used to infer the biomass and production of phytoplankton and bacteria. Phytoplankton PLFA were enriched within one day after label addition, whilst it took another 3 days before bacteria showed substantial enrichment. Group-specific primary production measurements revealed that coccolithophores showed higher primary production than green algae and diatoms. Elevated CO2 had a significant positive effect on post-bloom biomass of green algae, diatoms, and bacteria. A simple model based on measured isotope ratios of phytoplankton and bacteria revealed that CO2 had no significant effect on the carbon transfer efficiency from phytoplankton to bacteria during the bloom. There was no indication of CO2 effects on enhanced settling based on isotope mixing models during the phytoplankton bloom, but this could not be determined in the post-bloom phase. Our results suggest that CO2 effects are most pronounced in the post-bloom phase, under nutrient limitation.

Description: The uptake of anthropogenic CO2 by the oceans has led to a rise in the oceanic partial pressure of CO2, and to a decrease in pH and carbonate ion concentration. This modification of the marine carbonate system is referred to as ocean acidification. Numerous papers report the effects of ocean acidification on marine organisms and communities but few have provided details concerning full carbonate chemistry and complementary observations. Additionally, carbonate system variables are often reported in different units, calculated using different sets of dissociation constants and on different pH scales. Hence the direct comparison of experimental results has been problematic and often misleading. The need was identified to (1) gather data on carbonate chemistry, biological and biogeochemical properties, and other ancillary data from published experimental data, (2) transform the information into common framework, and (3) make data freely available. The present paper is the outcome of an effort to integrate ocean carbonate chemistry data from the literature which has been supported by the European Network of Excellence for Ocean Ecosystems Analysis (EUR-OCEANS) and the European Project on Ocean Acidification (EPOCA). A total of 185 papers were identified, 100 contained enough information to readily compute carbonate chemistry variables, and 81 data sets were archived at PANGAEA – The Publishing Network for Geoscientific & Environmental Data. This data compilation is regularly updated as an ongoing mission of EPOCA.

Description: Ancient Lake Ohrid is a steep-sided, oligotrophic, karst lake that was tectonically formed most likely within the Pliocene and often referred to as a hotspot of endemic biodiversity. This study aims on tracing significant lake level fluctuations at Lake Ohrid using high-resolution acoustic data in combination with lithological, geochemical, and chronological information from two sediment cores recovered from sub-aquatic terrace levels at ca. 32 and 60m water depth. According to our data, significant lake level fluctuations with prominent lowstands of ca. 60 and 35m below the present water level occurred during Marine Isotope Stage (MIS) 6 and MIS 5, respectively. The effect of these lowstands on biodiversity in most coastal parts of the lake is negligible, due to only small changes in lake surface area, coastline, and habitat. In contrast, biodiversity in shallower areas was more severely affected due to disconnection of today sublacustrine springs from the main water body. Multichannel seismic data from deeper parts of the lake clearly image several clinoform structures stacked on top of each other. These stacked clinoforms indicate significantly lower lake levels prior to MIS 6 and a stepwise rise of water level with intermittent stillstands since its existence as water-filled body, which might have caused enhanced expansion of endemic species within Lake Ohrid.

Description: CO2 emissions are leading to an acidification of the oceans. Predicting marine community vulnerability towards acidification is difficult, as adaptation processes cannot be accounted for in most experimental studies. Naturally CO2 enriched sites thus can serve as valuable proxies for future changes in community structure. Here we describe a natural analogue site in the Western Baltic Sea. Seawater pCO2 in Kiel Fjord is elevated for large parts of the year due to upwelling of CO2 rich waters. Peak pCO2 values of 〉230 Pa (〉2300 μatm) and pHNBS values of 〈7.5 are encountered during summer and autumn, average pCO2 values are ~70 Pa (~700 μatm). In contrast to previously described naturally CO2 enriched sites that have suggested a progressive displacement of calcifying auto- and heterotrophic species, the macrobenthic community in Kiel Fjord is dominated by calcifying invertebrates. We show that blue mussels from Kiel Fjord can maintain control rates of somatic and shell growth at a pCO2 of 142 Pa (1400 μatm, pHNBS = 7.7). Juvenile mussel recruitment peaks during the summer months, when high water pCO2 values of ~100 Pa (~1000 μatm) prevail. Our findings indicate that calcifying keystone species may be able to cope with surface ocean pHNBS values projected for the end of this century when food supply is sufficient. However, owing to non-linear synergistic effects of future acidification and upwelling of corrosive water, peak seawater pCO2 in Kiel Fjord and many other productive estuarine habitats could increase to values 〉400 Pa (〉4000 μatm). These changes will most likely affect calcification and recruitment, and increase external shell dissolution.

Description: Ocean acidification, as a consequence of increasing marine pCO2, may have severe effects on the physiology of marine organisms. However, experimental studies remain scarce, in particular concerning fish. While adults will most likely remain relatively unaffected by changes in seawater pH, early life-history stages are potentially more sensitive – particularly the critical stage of fertilization, in which sperm motility plays a central role. In this study, the effects of ocean acidification (decrease of pHT to 7.55) on sperm motility of Baltic cod, Gadus morhua, were assessed. We found no significant effect of decreased pH on sperm speed, rate of change of direction or percent motility for the population of cod analyzed. We predict that future ocean acidification will probably not pose a problem for sperm behavior, and hence fertilization success, of Baltic cod.

Description: A shallow-water area in the Santa Barbara Channel, California, known collectively as the Coal Oil Point seep field, is one of the largest natural submarine hydrocarbon emission areas in the world. Both gas and oil are seeping constantly through a predominantly sandy seabed into the ocean. This study focused on the methanotrophic activity within the surface sediments (0–15 cm) of the permeable seabed in the so-called Brian Seep area at a water depth of ~10 m. Detailed investigations of the sediment biogeochemistry of active gas vents indicated that it is driven by fast advective transport of water through the sands, resulting in a deep penetration of oxidants (oxygen, sulfate). Maxima of microbial methane consumption were found at the sediment-water interface and in deeper layers of the sediment, representing either aerobic or anaerobic oxidation of methane, respectively. Methane consumption was relatively low (0.6–8.7 mmolm−2 d−1) in comparison to gas hydratebearing fine-grained sediments on the continental shelf. The low rates and the observation of free gas migrating through permeable coastal sediments indicate that a substantial proportion of methane can escape the microbial methane filter in coastal sediments.

Description: Dimethylsulfoniopropionate (DMSP) is produced in surface seawater by phytoplankton. Phytoplankton culture experiments have shown that nanoeucaryotes (NANO) display much higher mean DMSP-to-Carbon or DMSP-to-Chlorophyll (Chl) ratios than Prochlorococcus (PRO), Synechococcus (SYN) or diatoms (DIAT). Moreover, the DMSP-lyase activity of algae which cleaves DMSP into dimethylsulfide (DMS) is even more group specific than DMSP itself. Ship-based observations have shown at limited spatial scales, that sea surface DMS-to-Chl ratios (DMS:Chl) are dependent on the composition of phytoplankton groups. Here we use satellite remote sensing of Chl (from SeaWiFS) and of Phytoplankton Group Dominance (PGD from PHYSAT) with ship-based sea surface DMS concentrations (8 cruises in total) to assess this dependence on an unprecedented spatial scale. PHYSAT provides PGD (either NANO, PRO, SYN, DIAT, Phaeocystis (PHAEO) or coccolithophores (COC)) in each satellite pixel (1/4° horizontal resolution). While there are identification errors in the PHYSAT method, it is important to note that these errors are lowest for NANO PGD which we typify by high DMSP:Chl. In summer, in the Indian sector of the Southern Ocean, we find that mean DMS:Chl associated with NANO + PHAEO and PRO + SYN + DIAT are 13.6±8.4 mmol g−1 (n=34) and 7.3±4.8 mmol g−1 (n=24), respectively. That is a statistically significant difference (P〈0.001) that is consistent with NANO and PHAEO being relatively high DMSP producers. However, in the western North Atlantic between 40° N and 60° N, we find no significant difference between the same PGD. This is most likely because coccolithophores account for the non-dominant part of the summer phytoplankton assemblages. Meridional distributions at 22° W in the Atlantic, and 95° W and 110° W in the Pacific, both show a marked drop in DMS:Chl near the equator, down to few mmol g−1, yet the basins exhibit different PGD (NANO in the Atlantic, PRO and SYN in the Pacific). In tropical and subtropical Atlantic and Pacific waters away from the equatorial and coastal upwelling, mean DMS:Chl associated with high and low DMSP producers are statistically significantly different, but the difference is opposite of that expected from culture experiments. Hence, in a majority of cases PGD is not of primary importance in controlling DMS:Chl variations. We therefore conclude that water-leaving radiance spectra obtained simultaneously from ocean color sensor measurements of Chl concentrations and dominant phytoplankton groups can not be used to predict global fields of DMS.

Description: Anthropogenic emissions of nitrogen (N) to the atmosphere have been strongly increasing during the last century, leading to greater atmospheric N deposition to the oceans. The North Atlantic subtropical gyre (NASTG) is particularly impacted. Here, upwind sources of anthropogenic N from North American and European sources have raised atmospheric N deposition to rates comparable with N2 fixation in the gyre. However, the biogeochemical fate of the deposited N is unclear because there is no detectable accumulation in the surface waters. Most likely, deposited N accumulates in the main thermocline instead, where there is a globally unique pool of N in excess of the canonical Redfield ratio of 16 N:1 phosphorus (P). To investigate this depth zone as a sink for atmospheric N, we used a biogeochemical ocean transport model and year 2000 nutrient deposition data. We examined the maximum effects of three mechanisms that may transport excess N from the ocean surface to the main thermocline: physical transport, preferential P remineralization of sinking particles, and nutrient uptake and export by phytoplankton at higher than Redfield N:P ratios. Our results indicate that atmospheric deposition may contribute 13-19% of the annual excess N input to the main thermocline. Modeled nutrient distributions in the NASTG were comparable to observations only when non-Redfield dynamics were invoked. Preferential P remineralization could not produce realistic results on its own; if it is an important contributor to ocean biogeochemistry, it must co-occur with N2 fixation. The results suggest that: 1) the main thermocline is an important sink for anthropogenic N deposition, 2) non-Redfield surface dynamics determine the biogeochemical fate of atmospherically deposited nutrients, and 3) atmospheric N accumulation in the main thermocline has long term impacts on surface ocean biology.

Description: The sea-surface microlayer (SML) is located within the boundary between the atmosphere and hydrosphere. The high spatial and temporal variability of the SML's properties, however, have hindered a clear understanding of interactions between biotic and abiotic parameters at or across the air-water interface. Among the factors changing the physical and chemical environment of the SML, wind speed is an important one. In order to examine the temporal effects of minimized wind influence, SML samples were obtained from the coastal zone of the southern Baltic Sea and from mesocosm experiments in a marina to study naturally and artificially calmed sea surfaces. Organic matter concentrations as well as abundance, (3)H-thymidine incorporation, and the community composition of bacteria in the SML (bacterioneuston) compared to the underlying bulk water (ULW) were analyzed. In all SML samples, dissolved organic carbon and nitrogen were only slightly enriched and showed low temporal variability, whereas particulate organic carbon and nitrogen were generally greatly enriched and highly variable. This was especially pronounced in a dense surface film (slick) that developed during calm weather conditions as well as in the artificially calmed mesocosms. Overall, bacterioneuston abundance and productivity correlated with changing concentrations of particulate organic matter. Moreover, changes in the community composition in the field study were stronger in the particle-attached than in the non-attached bacterioneuston. This implies that decreasing wind enhances the importance of particle-attached assemblages and finally induces a succession of the bacterial community in the SML. Eventually, under very calm meteorological conditions, there is an uncoupling of the bacterioneuston from the ULW.

Description: Emissions of sulphur hexafluoride (SF6), one of the strongest greenhouse gases on a per molecule basis, are targeted to be collectively reduced under the Kyoto Protocol. Because of its long atmospheric lifetime (estimated as 800 to 3200 years), the accumulation of SF6 in the atmosphere is a direct measure of its global emissions. Examination of our extended data set of globally distributed high-precision SF6 observations shows an increase in SF6 abundance from near zero in the 1970s to a global mean of 6.7 ppt by the end of 2008. In-depth evaluation of our long-term data records shows that the global source of SF6 decreased after 1995, most likely due to SF6 emission reductions in industrialised countries, but increased again after 1998. By subtracting those emissions reported by Annex I countries to the United Nations Framework Convention of Climatic Change (UNFCCC) from our observation-inferred SF6 source leaves a surprisingly large gap of more than 7080% of non-reported SF6 emissions in the last decade. This suggests a strong under-estimation of emissions in Annex I countries and underlines the urgent need for independent atmospheric verification of greenhouse gases emissions accounting.

Description: The recently increasing development of whole sky imagers enables temporal and spatial high-resolution sky observations. One application already performed in most cases is the estimation of fractional sky cover. A distinction between different cloud types, however, is still in progress. Here, an automatic cloud classification algorithm is presented, based on a set of mainly statistical features describing the color as well as the texture of an image. The k-nearest-neighbour classifier is used due to its high performance in solving complex issues, simplicity of implementation and low computational complexity. Seven different sky conditions are distinguished: high thin clouds (cirrus and cirrostratus), high patched cumuliform clouds (cirrocumulus and altocumulus), stratocumulus clouds, low cumuliform clouds, thick clouds (cumulonimbus and nimbostratus), stratiform clouds and clear sky. Based on the Leave-One-Out Cross-Validation the algorithm achieves an accuracy of about 97%. In addition, a test run of random images is presented, still outperforming previous algorithms by yielding a success rate of about 75%, or up to 88% if only "serious" errors with respect to radiation impact are considered. Reasons for the decrement in accuracy are discussed, and ideas to further improve the classification results, especially in problematic cases, are investigated.

Description: With the accumulation of anthropogenic carbon dioxide (CO2), a proceeding decline in seawater pH has been induced that is referred to as ocean acidification. The ocean's capacity for CO2 storage is strongly affected by biological processes, whose feedback potential is difficult to evaluate. The main source of CO2 in the ocean is the decomposition and subsequent respiration of organic molecules by heterotrophic bacteria. However, very little is known about potential effects of ocean acidification on bacterial degradation activity. This study reveals that the degradation of polysaccharides, a major component of marine organic matter, by bacterial extracellular enzymes was significantly accelerated during experimental simulation of ocean acidification. Results were obtained from pH perturbation experiments, where rates of extracellular α- and β-glucosidase were measured and the loss of neutral and acidic sugars from phytoplankton-derived polysaccharides was determined. Our study suggests that a faster bacterial turnover of polysaccharides at lowered ocean pH has the potential to reduce carbon export and to enhance the respiratory CO2 production in the future ocean.

Description: The Beta Triangle, a region of the oligotrophic subtropical eastern North Atlantic Ocean, is notorious for its enigmatic oxygen, carbon, and nitrogen balances, in which nutrient supply is said to explain only a fraction of production necessary for estimated carbon export. Rates of dissolved organic carbon accumulation and dissolved organic nitrogen utilization in surface water and an assessment of oxygen utilized, organic matter consumed, and nitrate and phosphate regenerated in subsurface water, show that conventional production estimates miss substantial shares of biotic production. The shallow export of total organic carbon, predominantly dissolved (DOC), by subduction is responsible for about 50–70% of apparent oxygen utilization in subsurface water between the base of the surface layer at ca. 140 m and ca. 195 m depth, but it is insignificant below. Additionally, there is an estimated accumulation of 1.0 to 1.75 mol DOC m−2 a−1 in surface water. Including DOC dynamics in its carbon balance reveals the surface of this ultra-oligotrophic part of the ocean to be net autotrophic. Increasing subsurface values of excess nitrogen (DINxs) imply the export of nitrogen from surface water stemming from production not exclusively fuelled by new nitrate supplied from below. Total organic nitrogen (almost exclusively dissolved, DON) is consumed in the surface layer at a rate estimated at 0.13 to 0.23 mol m−2 a−1. There is no variation in dissolved organic phosphorus (DOP) in the same direction. DON utilization thus contributes to the pronounced subsurface DINxs signature. DOC export and accumulation are important in the carbon balance in surface and near-surface water. DON utilization and, probably, N2 fixation contribute significant amounts to the nitrogen supply of surface water. These processes can close part of the enigmatic carbon and nitrogen balances in the Beta Triangle. There are, however, no comparable processes which can explain the equally enigmatic situation concerning phosphorus supply in this area.

Description: Water column data of carbon and carbon-relevant hydrographic and hydrochemical parameters from 188 previously non-publicly available cruise data sets in the Arctic Mediterranean Seas, Atlantic and Southern Ocean have been retrieved and merged into a new database: CARINA (CARbon dioxide IN the Atlantic Ocean). The data have gone through rigorous quality control procedures to assure the highest possible quality and consistency. The data for the pertinent parameters in the CARINA database were objectively examined in order to quantify systematic differences in the reported values, i.e. secondary quality control. Systematic biases found in the data have been corrected in the three data products: merged data files with measured, calculated and interpolated data for each of the three CARINA regions, i.e. the Arctic Mediterranean Seas, the Atlantic and the Southern Ocean. These products have been corrected to be internally consistent. Ninety-eight of the cruises in the CARINA database were conducted in the Atlantic Ocean, defined here as the region south of the Greenland-Iceland-Scotland Ridge and north of about 30° S. Here we present an overview of the Atlantic Ocean synthesis of the CARINA data and the adjustments that were applied to the data product. We also report the details of the secondary QC (Quality Control) for salinity for this data set. Procedures of quality control – including crossover analysis between stations and inversion analysis of all crossover data – are briefly described. Adjustments to salinity measurements were applied to the data from 10 cruises in the Atlantic Ocean region. Based on our analysis we estimate the internal consistency of the CARINA-ATL salinity data to be 4.1 ppm. With these adjustments the CARINA data products are consistent both internally as well as with GLODAP data, an oceanographic data set based on the World Hydrographic Program in the 1990s, and is now suitable for accurate assessments of, for example, oceanic carbon inventories and uptake rates and for model validation.

Description: Data on carbon and carbon-relevant hydrographic and hydrochemical parameters from 188 previously non-publicly available cruise data sets in the Artic Mediterranean Seas (AMS), Atlantic Ocean and Southern Ocean have been retrieved and merged to a new database: CARINA (CARbon IN the Atlantic Ocean). These data have gone through rigorous quality control (QC) procedures to assure the highest possible quality and consistency. The data for most of the measured parameters in the CARINA database were objectively examined in order to quantify systematic differences in the reported values. Systematic biases found in the data have been corrected in the data products, three merged data files with measured, calculated and interpolated data for each of the three CARINA regions; AMS, Atlantic Ocean and Southern Ocean. Out of a total of 188 cruise entries in the CARINA database, 59 reported pH measured values. All reported pH data have been unified to the Sea-Water Scale (SWS) at 25 C. Here we present details of the secondary QC of pH in the CARINA database and the scale unification to SWS at 25 C. The pH scale has been converted for 36 cruises. Procedures of quality control, including crossover analysis between cruises and inversion analysis are described. Adjustments were applied to the pH values for 21 of the cruises in the CARINA dataset. With these adjustments the CARINA database is consistent both internally as well as with the GLODAP data, an oceanographic data set based on the World Hydrographic Program in the 1990s. Based on our analysis we estimate the internal consistency of the CARINA pH data to be 0.005 pH units. The CARINA data are now suitable for accurate assessments of, for example, oceanic carbon inventories and uptake rates, for ocean acidification assessment and for model validation.

Description: Water column data of carbon and carbon relevant hydrographic and hydrochemical parameters have been retrieved from a large number of cruises and collected into a new database called CARINA (CARbon IN the Atlantic). These data have been merged into three sets of files, one for each of the three CARINA regions; the Arctic Mediterranean Seas (AMS), the Atlantic (ATL) and the Southern Ocean (SO). The first part of the CARINA database consists of three files, one for each CARINA region, containing the original, non-adjusted cruise data sets, including data quality flags for each measurement. These data have then been subject to rigorous quality control (QC) in order to ensure highest possible quality and consistency. The data for most of the parameters included were examined in order to quantify systematic biases in the reported values, i.e. secondary quality control. Significant biases have been corrected for in the second part of the CARINA data product. This consists of three files, one for each CARINA region, which contain adjustments to the original data values based on recommendations from the CARINA QC procedures, along with calculated and interpolated values for some missing parameters. Here we present an overview of the QC of the CFC data for the AMS region, including the chlorofluorocarbons CFC-11, CFC-12 and CFC-113, as well as carbon tetrachloride (CCl4). The Arctic Mediterranean Seas is comprised of the Arctic Ocean and the Nordic Seas, and the quality control was carried out separately in these two areas. For the secondary QC of the CFCs we used a combination of tools, including the evaluation of depth profiles and CFC ratios, surface saturations and a crossover analysis. This resulted in a multiplicative adjustment of data from some cruises, while other data were flagged to be of questionable quality, which excluded them from the final data product.

Description: Data on the carbon and carbon relevant hydrographic and hydrochemical parameters from previously not publicly available cruises in the Arctic, Atlantic and Southern Ocean have been retrieved and merged to a new data base: CARINA (CARbon IN the Atlantic). These data have gone through rigorous quality control (QC) procedures to assure the highest possible quality and consistency. All CARINA data were subject to primary QC; a process in which data are studied in order to identify outliers and obvious errors. Additionally, secondary QC was performed for several of the measured parameters in the CARINA data base. Secondary QC is a process in which the data are objectively studied in order to quantify systematic differences in the reported values. This process involved crossover analysis, and as a second step the offsets derived from the crossover analysis were used to calculate corrections of the parameters measured on individual cruises using least square models. Significant biases found in the data have been corrected in the data products, i.e. three merged data files containing measured, calculated and interpolated data for each of the three regions (i.e. Arctic Mediterranean Seas, Atlantic, and Southern Ocean). Here we report on the technical details of the quality control and on tools that have been developed and used during the project, including procedures for crossover analysis and least square models. Furthermore, an interactive website for uploading of results, plots, comments etc. was developed and was of critical importance for the success of the project, this is also described here.

Description: Carbon and carbon-relevant hydrographic and hydrochemical ancillary data from previously not publicly available cruises were retrieved and recently merged to a new data base, CARINA (CARbon IN the Atlantic). The initial North Atlantic project, an international effort for ocean carbon synthesis, was extended to include the Arctic Mediterranean Seas (Arctic Ocean and Nordic Seas) and all three sectors of the Southern Ocean. Of a total of 188 cruises, 37 cruises are part of the Southern Ocean. The present work focuses on data collected in the Indian sector (20° S–70° S; 30° E–150° E). The Southern Indian Ocean dataset covers the period 1992–2004 and includes seasonal repeated observations. Parameters including salinity, dissolved inorganic carbon (TCO2), total alkalinity (TA), oxygen, nitrate, phosphate and silicate were examined for cruise-to-cruise and overall consistency. In addition, data from an existing, quality controlled data base (GLODAP) were introduced in the CARINA analysis to improve data coverage in the Southern Ocean. A global inversion was performed to synthesize the information deduced from objective comparisons of deep measurements (〉1500 m) at nearby stations (generally 〈220 km). The corrections suggested by the inversion were allowed to vary within a fixed envelope, thus accounting for ocean interior variability. The adjustments applied to CARINA data and those recommended for GLODAP data, in order to obtain a consistent merged dataset, are presented and discussed. The final outcome of this effort is a new quality controlled data base for TCO2 and other properties of the carbon system that can now be used to investigate the natural variability or stability of ocean chemistry and the accumulation of anthropogenic carbon. This data product also offers an important new synthesis of seasonal to decadal observations to validate ocean biogeochemical models in a region where available historical data were very sparse.

Description: The original goal of the CARINA (Carbon in Atlantic Ocean) data synthesis project was to create a merged calibrated data set from open ocean subsurface measurements by European scientists that would be generally useful for biogeochemical investigations in the North Atlantic and in particular, studies involving the carbon system. Over time the geographic extent expanded to include the entire Atlantic, the Arctic and the Southern Ocean and the international collaboration broadened significantly. In this paper we give a brief history of the project, a general overview of data included and an outline of the procedures used during the synthesis. The end result of this project was a set of 3 data products, one for each of the listed ocean regions. It is critical that anyone who uses any of the CARINA data products recognize that the data products are not simply concatenations of the originally measured values. Rather, the data have been through an extensive calibration procedure designed to remove measurement bias and bad data. Also a significant fraction of the individual values in the data products were derived either by direct calculation or some means of approximation. These data products were constructed for basin scale biogeochemical investigations and may be inappropriate for investigations involving small areal extent or similar detailed analyses. More information on specific parts of this project can be found in companion articles in this issue. In particular, Tanhua et al. (2010) and Tanhua (2009) describe the procedures and software used to remove measurement bias from the original data. The three data products and a significant volume of supporting information are available from the CARINA web site hosted by the Carbon Dioxide Information Analysis Center (CDIAC: http://cdiac.esd.ornl.gov/oceans/CARINA/Carina_inv.html). Anyone wanting to use the data is advised to get the highest version number of each data product. Incremental versions represent either corrections or additions. The web site documents specifics of the changes.

Description: Coccolithophores play an important role in organic matter export due to their production of the mineral calcite that can act as ballast. Recent studies indicated that calcification in coccolithophores may be affected by changes in seawater carbonate chemistry. We investigated the influence of CO2 on the aggregation and sinking behaviour of the coccolithophore Emiliania huxleyi (PML B92/11) during a laboratory experiment. The coccolithophores were grown under low (~180 μatm), medium (~380 μatm), and high (~750 μatm) CO2 conditions. Aggregation of the cells was promoted using roller tables. Size and settling velocity of aggregates were determined during the incubation using video image analysis. Our results indicate that aggregate properties are sensitive to changes in the degree of ballasting, as evoked by ocean acidification. Average sinking velocity was highest for low CO2 aggregates (~1292 m d−1) that also had the highest particulate inorganic to particulate organic carbon (PIC/POC) ratio. Lowest PIC/POC ratios and lowest sinking velocity (~366 m d−1) at comparable sizes were observed for aggregates of the high CO2 treatment. Aggregates of the high CO2 treatment showed a 4-fold lower excess density (~4.2×10−4 g cm−3) when compared to aggregates from the medium and low CO2 treatments (~1.7 g×10−3 cm−3). We also observed that more aggregates formed in the high CO2 treatment, and that those aggregates contained more bacteria than aggregates in the medium and low CO2 treatment. If applicable to the future ocean, our findings suggest that a CO2 induced reduction of the calcite content of aggregates could weaken the deep export of organic matter in the ocean, particularly in areas dominated by coccolithophores.

Description: To indentify sources and transport mechanisms of iron in a coastal marine environment, we conducted measurements of the physiochemical speciation of Fe in the euphotic zone at three different locations in the Baltic Sea. In addition to sampling across a salinity gradient, we conducted this study over the spring and summer season. Moving from the riverine input characterized low salinity Bothnian Sea, via the Landsort Deep near Stockholm, towards the Gotland Deep in the Baltic Proper, total Fe concentrations averaged 114, 44, and 15 nM, respectively. At all three locations, a decrease in total Fe of 80–90% from early spring to summer was observed. Particulate Fe (PFe) was the dominating phase at all stations and accounted for 75–85% of the total Fe pool on average. The Fe isotope composition (δ 56Fe) of the PFe showed constant positive values in the Bothnian Sea surface waters (+0.08 to +0.20‰). Enrichment of heavy Fe in the Bothnian Sea PFe is possibly associated to input of aggregated land derived Fe-oxyhydroxides and oxidation of dissolved Fe(II). At the Landsort Deep the isotopic fractionation of PFe changed between −0.08‰ to +0.28‰ over the sampling period. The negative values in early spring indicate transport of PFe from the oxic-anoxic boundary at ∼80 m depth. The average colloidal iron fraction (CFe) showed decreasing concentrations along the salinity gradient; Bothnian Sea 15 nM; Landsort Deep 1 nM, and Gotland Deep 0.5 nM. Field Flow Fractionation data indicate that the main colloidal carrier phase for Fe in the Baltic Sea is a carbon-rich fulvic acid associated compound, likely of riverine origin. A strong positive correlation between PFe and chl-a indicates that cycling of suspended Fe is at least partially controlled by primary production. However, this relationship may not be dominated by active uptake of Fe into phytoplankton, but instead may reflect scavenging and removal of PFe during phytoplankton sedimentation.

Description: Future climate change as a result of increasing atmospheric CO2 concentrations is expected to strongly affect the oceans, with shallower winter mixing and consequent reduction in primary production and oceanic carbon drawdown in low and mid-latitudinal oceanic regions. Here we test this hypothesis by examining the effects of cold and warm winters on the carbonate system in the surface waters of the Northeast Atlantic Ocean for the period between 2005 and 2007. Monthly observations were made between the English Channel and the Bay of Biscay using a ship of opportunity program. During the colder winter of 2005/2006, the maximum depth of the mixed layer reached up to 650 m in the Bay of Biscay, whilst during the warmer (by 2.6 a± 0.5 a°C) winter of 2006/2007 the mixed layer depth reached only 300 m. The inter-annual differences in late winter concentrations of nitrate (2.8 ± 1.1 μmol l−1) and dissolved inorganic carbon (22 a± 6 μmol kg−1, with higher concentrations at the end of the colder winter (2005/2006), led to differences in the dissolved oxygen anomaly and the chlorophyll 〈i>α〈/i>-fluorescence data for the subsequent growing season. In contrast to model predictions, the calculated air-sea CO2 fluxes (ranging from +3.7 to ĝ̂'4.8 mmol mĝ̂'2 d−1) showed an increased oceanic CO2 uptake in the Bay of Biscay following the warmer winter of 2006/2007 associated with wind speed and sea surface temperature differences. ©Author(s) 2010. CC Attribution 3.0 License.

Description: Dissolved CH4 was measured in the water column at the Boknis Eck (BE) time series station in the Eckernförde Bay (SW Baltic Sea) on a monthly basis from June 2006 to November 2008. The water column at BE was always supersaturated with CH4 and, therefore, CH4 was released to the atmosphere throughout the sampling period: the mean CH4 surface (1 m) saturation at BE was 554±317%. A pulse of enhanced CH4 emissions occurs when the CH4 accumulation in the hypoxic bottom layer during summer is terminated in late summer/autumn. We did not detect a straightforward relationship between periods of enhanced CH4 in the bottom layer and hypoxic events at BE: the sedimentary release of CH4 seemed to be mainly triggered by sedimenting organic material from phytoplankton blooms. We conclude that future CH4 emissions from BE will be determined by the intensity of phytoplankton blooms, which in turn will be influenced by eutrophication. However, hypoxic events seem to have only a modulating effect on the enhancement of sedimentary methanogenesis and the subsequent release of CH4 to the water column.

Description: Water column data of carbon and carbon-relevant parameters have been collected and merged into a new database called CARINA (CARbon IN the Atlantic). In order to provide a consistent data set, all data have been examined for systematic biases and adjusted if necessary (secondary quality control (QC)). The CARINA data set is divided into three regions: the Arctic/Nordic Seas, the Atlantic region and the Southern Ocean. Here we present the CFC data for the Atlantic region, including the chlorofluorocarbons CFC-11, CFC-12 and CFC-113 as well as carbon tetrachloride (CCl4). The methods applied for the secondary quality control, a crossover analyses, the investigation of CFC ratios in the ocean and the CFC surface saturation are presented. Based on the results, the CFC data of some cruises are adjusted by a certain factor or given a “poor” quality flag.

Description: Based on an international workshop (Gothenburg, 14–16 May 2008), this review article aims to combine interdisciplinary knowledge from coastal and open ocean research on iron biogeochemistry. The major scientific findings of the past decade are structured into sections on natural and artificial iron fertilization, iron inputs into coastal and estuarine systems, colloidal iron and organic matter, and biological processes. Potential effects of global climate change, particularly ocean acidification, on iron biogeochemistry are discussed. The findings are synthesized into recommendations for future research areas.

Description: There is an international commitment to develop a comprehensive, coordinated and sustained ocean observation system. However, a foundation for any observing, monitoring or research effort is effective and reliable in situ sensor technologies that accurately measure key environmental parameters. Ultimately, the data used for modelling efforts, management decisions and rapid responses to ocean hazards are only as good as the instruments that collect them. There is also a compelling need to develop and incorporate new or novel technologies to improve all aspects of existing observing systems and meet various emerging challenges. Assessment of Sensor Performance was a cross-cutting issues session at the international OceanSensors08 workshop in Warnemünde, Germany, which also has penetrated some of the papers published as a result of the workshop (Denuault, 2009; Kröger et al., 2009; Zielinski et al., 2009). The discussions were focused on how best to classify and validate the instruments required for effective and reliable ocean observations and research. The following is a summary of the discussions and conclusions drawn from this workshop, which specifically addresses the characterisation of sensor systems, technology readiness levels, verification of sensor performance and quality management of sensor systems.

Description: Here we present an equation for the estimation of nitrate in surface waters of the North Atlantic Ocean (40° N to 52° N, 10° W to 60° W). The equation was derived by multiple linear regression (MLR) from nitrate, sea surface temperature (SST) observational data and model mixed layer depth (MLD) data. The observational data were taken from merchant vessels that have crossed the North Atlantic on a regular basis in 2002/2003 and from 2005 to the present. It is important to find a robust and realistic estimate of MLD because the deepening of the mixed layer is crucial for nitrate supply to the surface. We compared model data from two models (FOAM and Mercator) with MLD derived from float data (using various criteria). The Mercator model gives a MLD estimate that is close to the MLD derived from floats. MLR was established using SST, MLD from Mercator, time and latitude as predictors. Additionally a neural network was trained with the same dataset and the results were validated against both model data as a "ground truth" and an independent observational dataset. This validation produced RMS errors of the same order for MLR and the neural network approach. We conclude that it is possible to estimate nitrate concentrations with an uncertainty of ±1.4 μmol L−1 in the North Atlantic.

Description: During the cold period of the Last Glacial Maximum (LGM, about 21 000 years ago) atmospheric CO2 was around 190 ppm, much lower than the pre-industrial concentration of 280 ppm. The causes of this substantial drop remain partially unresolved, despite intense research. Understanding the origin of reduced atmospheric CO2 during glacial times is crucial to comprehend the evolution of the different carbon reservoirs within the Earth system (atmosphere, terrestrial biosphere and ocean). In this context, the ocean is believed to play a major role as it can store large amounts of carbon, especially in the abyss, which is a carbon reservoir that is thought to have expanded during glacial times. To create this larger reservoir, one possible mechanism is to produce very dense glacial waters, thereby stratifying the deep ocean and reducing the carbon exchange between the deep and upper ocean. The existence of such very dense waters has been inferred in the LGM deep Atlantic from sediment pore water salinity and δ18O inferred temperature. Based on these observations, we study the impact of a brine mechanism on the glacial carbon cycle. This mechanism relies on the formation and rapid sinking of brines, very salty water released during sea ice formation, which brings salty dense water down to the bottom of the ocean. It provides two major features: a direct link from the surface to the deep ocean along with an efficient way of setting a strong stratification. We show with the CLIMBER-2 carbon-climate model that such a brine mechanism can account for a significant decrease in atmospheric CO2 and contribute to the glacial-interglacial change. This mechanism can be amplified by low vertical diffusion resulting from the brine-induced stratification. The modeled glacial distribution of oceanic δ13C as well as the deep ocean salinity are substantially improved and better agree with reconstructions from sediment cores, suggesting that such a mechanism could have played an important role during glacial times.