ALBERT

Description: Well water level changes associated with magmatic unrest can be interpreted as a result of pore pressure changes in the aquifer due to crustal deformation, and so could provide constraints on the subsurface processes causing this strain. We use finite element analysis to demonstrate the response of aquifers to volumetric strain induced by pressurized magma reservoirs. Two different aquifers are invoked – an unconsolidated pyroclastic deposit and a vesicular lava flow – and embedded in an impermeable crust, overlying a magma chamber. The time-dependent, fully coupled models simulate crustal deformation accompanying chamber pressurization and the resulting hydraulic head changes as well as flow through the porous aquifer, i.e. porous flow. The simulated strain leads to centimetres (pyroclastic aquifer) to metres (lava flow aquifer) of hydraulic head changes; both strain and hydraulic head change with time due to substantial porous flow in the hydrological system. Well level changes are particularly sensitive to chamber volume, shape and pressurization strength, followed by aquifer permeability and the phase of the pore fluid. The depths of chamber and aquifer, as well as the aquifer's Young's modulus also have significant influence on the hydraulic head signal. While source characteristics, the distance between chamber and aquifer and the elastic stratigraphy determine the strain field and its partitioning, flow and coupling parameters define how the aquifer responds to this strain and how signals change with time. We find that generic analytical models can fail to capture the complex pre-eruptive subsurface mechanics leading to strain-induced well level changes, due to aquifer pressure changes being sensitive to chamber shape and lithological heterogeneities. In addition, the presence of a pore fluid and its flow have a significant influence on the strain signal in the aquifer and are commonly neglected in analytical models. These findings highlight the need for numerical models for the interpretation of observed well level signals. However, simulated water table changes do indeed mirror volumetric strain, and wells are therefore a valuable addition to monitoring systems that could provide important insights into pre-eruptive dynamics.

Description: The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 μmol O2 L−1) and hypoxic (〈 63 μmol O2 L−1) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 μmol L−1 even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol m−2 d−1 on average in the oxic zone, to 7 mmol m−2 d−1 on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol m−2 d−1), but declined to 1.3 mmol m−2 d−1 in bottom waters with oxygen concentrations below 20 μmol L−1. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic–hypoxic zone, to 10 % in the hypoxic–anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.

Description: Based upon thermal-infrared satellite imagery in combination with ERA-Interim atmospheric reanalysis data, we derive long-term polynya characteristics such as polynya area, thin-ice thickness distribution, and ice-production rates for a 13-year investigation period (2002–2014) for the austral winter (1 April to 30 September) in the Antarctic southern Weddell Sea. All polynya parameters are derived from daily cloud-cover corrected thin-ice thickness composites. The focus lies on coastal polynyas which are important hot spots for new-ice formation, bottom-water formation, and heat/moisture release into the atmosphere. MODIS has the capability to resolve even very narrow coastal polynyas. Its major disadvantage is the sensor limitation due to cloud cover. We make use of a newly developed and adapted spatial feature reconstruction scheme to account for cloud-covered areas. We find the sea-ice areas in front of the Ronne and Brunt ice shelves to be the most active with an annual average polynya area of 3018 ± 1298 and 3516 ± 1420 km2 as well as an accumulated volume ice production of 31 ± 13 and 31 ± 12 km3, respectively. For the remaining four regions, estimates amount to 421 ± 294 km2 and 4 ± 3 km3 (Antarctic Peninsula), 1148 ± 432 km2 and 12 ± 5 km3 (iceberg A23A), 901 ± 703 km2 and 10 ± 8 km3 (Filchner Ice Shelf), as well as 499 ± 277 km2 and 5 ± 2 km3 (Coats Land). Our findings are discussed in comparison to recent studies based on coupled sea-ice/ocean models and passive-microwave satellite imagery, each investigating different parts of the southern Weddell Sea.

Description: The ocean is a substantial source of nitrous oxide (N2O) to the atmosphere, but little is known about how this flux might change in the future. Here, we investigate the potential evolution of marine N2O emissions in the 21st century in response to anthropogenic climate change using the global ocean biogeochemical model NEMO-PISCES. Assuming nitrification as the dominant N2O formation pathway, we implemented two different parameterizations of N2O production which differ primarily under low-oxygen (O2) conditions. When forced with output from a climate model simulation run under the business-as-usual high-CO2 concentration scenario (RCP8.5), our simulations suggest a decrease of 4 to 12 % in N2O emissions from 2005 to 2100, i.e., a reduction from 4.03/3.71 to 3.54/3.56 TgN yr−1 depending on the parameterization. The emissions decrease strongly in the western basins of the Pacific and Atlantic oceans, while they tend to increase above the oxygen minimum zones (OMZs), i.e., in the eastern tropical Pacific and in the northern Indian Ocean. The reduction in N2O emissions is caused on the one hand by weakened nitrification as a consequence of reduced primary and export production, and on the other hand by stronger vertical stratification, which reduces the transport of N2O from the ocean interior to the ocean surface. The higher emissions over the OMZ are linked to an expansion of these zones under global warming, which leads to increased N2O production, associated primarily with denitrification. While there are many uncertainties in the relative contribution and changes in the N2O production pathways, the increasing storage seems unequivocal and determines largely the decrease in N2O emissions in the future. From the perspective of a global climate system, the averaged feedback strength associated with the projected decrease in oceanic N2O emissions amounts to around −0.009 W m−2 K−1, which is comparable to the potential increase from terrestrial N2O sources. However, the assessment for a potential balance between the terrestrial and marine feedbacks calls for an improved representation of N2O production terms in fully coupled next-generation Earth system models.

Description: Coastal zones are important source regions for a variety of trace gases including halocarbons and sulphur-bearing species. While salt-marshes, macroalgae and phytoplankton communities have been intensively studied, little is known about trace gas fluxes in seagrass meadows. Here we report results of a newly developed dynamic flux chamber system that can be deployed in intertidal areas over full tidal cycles allowing for high time resolved measurements. The trace gases measured in this study included carbon dioxide (CO2), methane (CH4) and a variety of hydrocarbons, halocarbons and sulphur-bearing compounds. The high time resolved CO2 and CH4 flux measurements revealed a complex dynamic mediated by tide and light. In contrast to most previous studies our data indicate significantly enhanced fluxes during tidal immersion relative to periods of air exposure. Short emission peaks occured with onset of the feeder current at the sampling site. We suggest an overall strong effect of advective transport processes to explain the elevated fluxes during tidal immersion. Many emission estimates from tidally influenced coastal areas still rely on measurements carried out during low tide only. Hence, our results may have significant implications for budgeting trace gases in coastal areas. This dynamic flux chamber system provides intensive time series data of community respiration (at night) and net community production (during the day) of shallow coastal systems.

Description: In this study we present gas-exchange measurements conducted in a large-scale wind–wave tank. Fourteen chemical species spanning a wide range of solubility (dimensionless solubility, α = 0.4 to 5470) and diffusivity (Schmidt number in water, Scw = 594 to 1194) were examined under various turbulent (u10 = 0.73 to 13.2 m s−1) conditions. Additional experiments were performed under different surfactant modulated (two different concentration levels of Triton X-100) surface states. This paper details the complete methodology, experimental procedure and instrumentation used to derive the total transfer velocity for all examined tracers. The results presented here demonstrate the efficacy of the proposed method, and the derived gas-exchange velocities are shown to be comparable to previous investigations. The gas transfer behaviour is exemplified by contrasting two species at the two solubility extremes, namely nitrous oxide (N2O) and methanol (CH3OH). Interestingly, a strong transfer velocity reduction (up to a factor of 3) was observed for the relatively insoluble N2O under a surfactant covered water surface. In contrast, the surfactant effect for CH3OH, the high solubility tracer, was significantly weaker

Description: Bromoform (CHBr3) is one important precursor of atmospheric reactive bromine species that are involved in ozone depletion in the troposphere and stratosphere. In the open ocean bromoform production is linked to phytoplankton that contains the enzyme bromoperoxidase. Coastal sources of bromoform are higher than open ocean sources. However, open ocean emissions are important because the transfer of tracers into higher altitude in the air, i.e. into the ozone layer, strongly depends on the location of emissions. For example, emissions in the tropics are more rapidly transported into the upper atmosphere than emissions from higher latitudes. Global spatio-temporal features of bromoform emissions are poorly constrained. Here, a global three-dimensional ocean biogeochemistry model (MPIOM-HAMOCC) is used to simulate bromoform cycling in the ocean and emissions into the atmosphere using recently published data of global atmospheric concentrations (Ziska et al., 2013) as upper boundary conditions. Our simulated surface concentrations of CHBr3 match the observations well. Simulated global annual emissions based on monthly mean model output are lower than previous estimates, including the estimate by Ziska et al. (2013), because the gas exchange reverses when less bromoform is produced in non-blooming seasons. This is the case for higher latitudes, i.e. the polar regions and northern North Atlantic. Further model experiments show that future model studies may need to distinguish different bromoform-producing phytoplankton species and reveal that the transport of CHBr3 from the coast considerably alters open ocean bromoform concentrations, in particular in the northern sub-polar and polar regions.

Description: In this study we report fluxes of chloromethane (CH3Cl), bromomethane (CH3Br), iodomethane (CH3I), and bromoform (CHBr3) from two sampling campaigns (summer and spring) in the seagrass dominated subtropical lagoon Ria Formosa, Portugal. Dynamic flux chamber measurements were performed when seagrass patches were either air-exposed or submerged. Overall, we observed highly variable fluxes from the seagrass meadows and attributed them to diurnal cycles, tidal effects, and the variety of possible sources and sinks in the seagrass meadows. The highest emissions with up to 130 nmol m−2 h−1 for CH3Br were observed during tidal changes, from air exposure to submergence and conversely. Furthermore, during the spring campaign, the emissions of halocarbons were significantly elevated during tidal inundation as compared to air exposure. Accompanying water sampling performed during both campaigns revealed elevated concentrations of CH3Cl and CH3Br, indicating productive sources within the lagoon. Stable carbon isotopes of halocarbons from the air and water phase along with source signatures were used to allocate the distinctive sources and sinks in the lagoon. Results suggest that CH3Cl was rather originating from seagrass meadows and water column than from salt marshes. Aqueous and atmospheric CH3Br was substantially enriched in 13C in comparison to source signatures for seagrass meadows and salt marshes. This suggests a significant contribution from the water phase on the atmospheric CH3Br in the lagoon. A rough global upscaling yields annual productions from seagrass meadows of 2.3–4.5 Gg yr−1, 0.5–1.0 Gg yr−1, 0.6–1.2 Gg yr−1, and 1.9–3.7 Gg yr−1 for CH3Cl, CH3Br, CH3I, and CHBr3 respectively. This suggests a minor contribution from seagrass meadows to the global production of CH3Cl and CH3Br with about 0.1 and 0.7%, respectively. In comparison to the known marine sources for CH3I and CHBr3, seagrass meadows are rather small sources.

Description: Constraints on the Mediterranean Sea's storage of anthropogenic CO2 are limited, coming only from data-based approaches that disagree by more than a factor of two. Here we simulate this marginal sea's anthropogenic carbon storage by applying a perturbation approach in a high-resolution regional model. Our model simulates that, between 1800 and 2001, basin-wide CO2 storage by the Mediterranean Sea has increased by 1.0 Pg C, a lower limit based on the model's weak deep-water ventilation, as revealed by evaluation with CFC-12. Furthermore, by testing a data-based approach (transit time distribution) in our model, comparing simulated anthropogenic CO2 to values computed from simulated CFC-12 and physical variables, we conclude that the associated basin-wide storage of 1.7 Pg, published previously, must be an upper bound. Out of the total simulated storage of 1.0 Pg C, 75% comes from the air-sea flux into the Mediterranean Sea and 25% comes from net transport from the Atlantic across the Strait of Gibraltar. Sensitivity tests indicate that the Mediterranean Sea's higher total alkalinity, relative to the global-ocean mean, enhances the Mediterranean's total inventory of anthropogenic carbon by 10%. Yet the corresponding average anthropogenic change in surface pH does not differ significantly from the global-ocean average, despite higher total alkalinity. In Mediterranean deep waters, the pH change is estimated to be between -0.005 and -0.06 pH units.

Description: To assess potential impacts of climate change for a specific location, one typically employs climate model simulations at the grid box corresponding to the same geographical location. But based on regional climate model simulations, we show that simulated climate might be systematically displaced compared to observations. In particular in the rain shadow of moutain ranges, a local grid box is therefore often not representative of observed climate: the simulated windward weather does not flow far enough across the mountains; local grid boxes experience the wrong airmasses and atmospheric circulation. In some cases, also the local climate change signal is deteriorated. Classical bias correction methods fail to correct these location errors. Often, however, a distant simulated time series is representative of the considered observed precipitation, such that a non-local bias correction is possible. These findings also clarify limitations of bias correcting global model errors, and of bias correction against station data.

Description: Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I) and diiodomethane (CH2I2). Enhanced biological production during the Atlantic Cold Tongue (ACT) season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 and up to 9.2 pmol L−1 for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water, CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol L−1 in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol L−1. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and one of the main driving factors of their emissions into the atmosphere in the ACT-region. The calculated production rates of the compounds in the mixed layer are 34 ± 65 pmol m−3 h−1 for CHBr3, 10 ± 12 pmol m−3 h−1 for CH2Br2, 21 ± 24 pmol m−3 h−1 for CH3I and 384 ± 318 pmol m−3 h−1 for CH2I2 determined from 13 depth profiles.

Description: Ocean acidification is expected to influence plankton community structure and biogeochemical element cycles. To date, the response of plankton communities to elevated CO2 has been studied primarily during nutrient-stimulated blooms. In this CO2 manipulation study, we used large-volume (~ 55 m3) pelagic in situ mesocosms to enclose a natural summer, post-spring-bloom plankton assemblage in the Baltic Sea to investigate the response of organic matter pools to ocean acidification. The carbonate system in the six mesocosms was manipulated to yield average fCO2 ranging between 365 and ~ 1230 μatm with no adjustment of naturally available nutrient concentrations. Plankton community development and key biogeochemical element pools were subsequently followed in this nitrogen-limited ecosystem over a period of 7 weeks. We observed higher sustained chlorophyll a and particulate matter concentrations (~ 25 % higher) and lower inorganic phosphate concentrations in the water column in the highest fCO2 treatment (1231 μatm) during the final 2 weeks of the study period (Phase III), when there was low net change in particulate and dissolved matter pools. Size-fractionated phytoplankton pigment analyses indicated that these differences were driven by picophytoplankton (〈 2 μm) and were already established early in the experiment during an initial warm and more productive period with overall elevated chlorophyll a and particulate matter concentrations. However, the influence of picophytoplankton on bulk organic matter pools was masked by high biomass of larger plankton until Phase III, when the contribution of the small size fraction (〈 2 μm) increased to up to 90 % of chlorophyll a. In this phase, a CO2-driven increase in water column particulate carbon did not lead to enhanced sinking material flux but was instead reflected in increased dissolved organic carbon concentrations. Hence ocean acidification may induce changes in organic matter partitioning in the upper water column during the low-nitrogen summer period in the Baltic Sea.

Description: Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates, consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuel combustion and cement production (EFF) are based on energy statistics and cement production data, respectively, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover-change (some including nitrogen–carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2004–2013), EFF was 8.9 ± 0.4 GtC yr−1, ELUC 0.9 ± 0.5 GtC yr−1, GATM 4.3 ± 0.1 GtC yr−1, SOCEAN 2.6 ± 0.5 GtC yr−1, and SLAND 2.9 ± 0.8 GtC yr−1. For year 2013 alone, EFF grew to 9.9 ± 0.5 GtC yr−1, 2.3% above 2012, continuing the growth trend in these emissions, ELUC was 0.9 ± 0.5 GtC yr−1, GATM was 5.4 ± 0.2 GtC yr−1, SOCEAN was 2.9 ± 0.5 GtC yr−1, and SLAND was 2.5 ± 0.9 GtC yr−1. GATM was high in 2013, reflecting a steady increase in EFF and smaller and opposite changes between SOCEAN and SLAND compared to the past decade (2004–2013). The global atmospheric CO2 concentration reached 395.31 ± 0.10 ppm averaged over 2013. We estimate that EFF will increase by 2.5% (1.3–3.5%) to 10.1 ± 0.6 GtC in 2014 (37.0 ± 2.2 GtCO2 yr−1), 65% above emissions in 1990, based on projections of world gross domestic product and recent changes in the carbon intensity of the global economy. From this projection of EFF and assumed constant ELUC for 2014, cumulative emissions of CO2 will reach about 545 ± 55 GtC (2000 ± 200 GtCO2) for 1870–2014, about 75% from EFF and 25% from ELUC. This paper documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this living data set (Le Quéré et al., 2013, 2014). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP_2014).

Description: Cold-water corals are important habitat formers in deep-water ecosystems and at high latitudes. Ocean acidification and the resulting change in aragonite saturation are expected to affect these habitats and impact coral growth. Counter to expectations, the impact of saturation changes on the deep water coral Lophelia pertusa has been found to be less than expected, with the species sustaining growth even in undersaturated conditions. However, it is important to know whether such acclimation modifies the skeleton and thus its ecosystem functioning. Here we used Synchrotron X-Ray Tomography and Raman spectroscopy to examine changes in skeleton morphology and fibre orientation. We combined the morphological assessment with boron isotope analysis to determine if changes in growth are related to changes in control of calcification pH. Skeletal morphology is highly variable without clear changes in different saturation states. Raman investigations found no difference in macromorphological skeletal arrangement of early mineralization zones and secondary thickening between the treatments but revealed that the skeletal organic matrix layers were less distinct. The δ11B analyses show that L. pertusa up-regulates the internal calcifying fluid pH (pHcf) during calcification with disregard to ambient seawater pH and suggests that well-fed individuals can sustain a high internal pHcf. This indicates that any extra energetic demand required for calcification at low saturation is not detrimental to the skeletal morphology.

Description: Nitric oxide (NO) is a short-lived intermediate of the oceanic nitrogen cycle, however, due to its high reactivity, measurements of dissolved NO in seawater are rare. Here we present an improved method to determine NO concentrations in discrete seawater samples. The set-up of our system consisted of a chemiluminescence NO analyser connected to a stripping unit. The limit of detection for our method was 5 pmol NO in aqueous solution which translates into 0.25 nmol L−1 when using a 20 mL seawater sample volume. Our method was applied to measure high resolution depth profiles of dissolved NO during a cruise to the eastern tropical South Pacific Ocean. Our method is fast and comparably easy to handle thus it opens the door for deciphering the distribution of NO in the ocean and it facilitates laboratory studies on NO pathways.

Description: The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in a batch process for 552 samples collected during two cruises in the northeastern Atlantic and Nordic Seas from June to August 2012. One cruise was part of the UK Ocean Acidification research programme, and the other was a repeat hydrographic transect of the Extended Ellett Line. In combination with measurements made of other variables on these and other cruises, these data can be used to constrain the anthropogenic component of dissolved inorganic carbon (DIC) in the interior ocean, and to help to determine the influence of biological carbon uptake on surface ocean carbonate chemistry. The measurements have been processed, quality-controlled and submitted to an in-preparation global compilation of seawater δ13CDIC data, and are available from the British Oceanographic Data Centre. The observed δ13CDIC values fall in a range from g-0.58 to +2.37 ‰, relative to the Vienna Pee Dee Belemnite standard. The mean of the absolute differences between samples collected in duplicate in the same container type during both cruises and measured consecutively is 0.10 ‰, which corresponds to a μ uncertainty of 0.09 ‰, and which is within the range reported by other published studies of this kind. A crossover analysis was performed with nearby historical δ13CDIC data, indicating that any systematic offsets between our measurements and previously published results are negligible. Data doi.org/10.5285/09760a3a-c2b5-250b-e053-6c86abc037c0 (northeastern Atlantic), doi.org/10.5285/09511dd0-51db-0e21-e053-6c86abc09b95 (Nordic Seas).

Description: Marine-produced short-lived trace gases such as dibromomethane (CH2Br2), bromoform (CHBr3), methyliodide (CH3I) and dimethyl sulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry) with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model real-time conditions at the ocean surface and in the atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of very short-lived substances (VSLS). We show that differences between prescribing emissions and prescribing concentrations (−28 % for CH2Br2 to +11 % for CHBr3) result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air–sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air–sea transfer velocity (k) parameterizations, which was performed here for eight different parameterizations. The testing of these different k values is of special interest for DMS, as recently published parameterizations derived by direct flux measurements using eddy covariance measurements suggest decreasing k values at high wind speeds or a linear relationship with wind speed. Implementing these parameterizations reduces discrepancies in modelled DMS atmospheric mixing ratios and observations by a factor of 1.5 compared to parameterizations with a quadratic or cubic relationship to wind speed.

Description: An approach is proposed to assess hydrological simulation uncertainty originating from internal atmospheric variability. The latter is one of three major factors contributing to uncertainty of simulated climate change projections (along with so-called "forcing" and "climate model" uncertainties). Importantly, the role of internal atmospheric variability is most visible over spatio-temporal scales of water management in large river basins. Internal atmospheric variability is represented by large ensemble simulations (45 members) with the ECHAM5 atmospheric general circulation model. Ensemble simulations are performed using identical prescribed lower boundary conditions (observed sea surface temperature, SST, and sea ice concentration, SIC, for 1979–2012) and constant external forcing parameters but different initial conditions of the atmosphere. The ensemble of bias-corrected ECHAM5 outputs and ensemble averaged ECHAM5 output are used as a distributed input for the ECOMAG and SWAP hydrological models. The corresponding ensembles of runoff hydrographs are calculated for two large rivers of the Arctic basin: the Lena and Northern Dvina rivers. A number of runoff statistics including the mean and the standard deviation of annual, monthly and daily runoff, as well as annual runoff trend, are assessed. Uncertainties of runoff statistics caused by internal atmospheric variability are estimated. It is found that uncertainty of the mean and the standard deviation of runoff has a significant seasonal dependence on the maximum during the periods of spring–summer snowmelt and summer–autumn rainfall floods. Noticeable nonlinearity of the hydrological models' results in the ensemble ECHAM5 output is found most strongly expressed for the Northern Dvina River basin. It is shown that the averaging over ensemble members effectively filters the stochastic term related to internal atmospheric variability. Simulated discharge trends are close to normally distributed around the ensemble mean value, which fits well to empirical estimates and, for the Lena River, indicates that a considerable portion of the observed trend can be externally driven.

Description: Burial of organic carbon in marine sediments has a profound influence in marine biogeochemical cycles and provides a sink for greenhouse gases such as CO2 and CH4. However, tracing organic carbon from primary production sources as well as its transformations in the sediment record remains challenging. Here we examine a novel but growing tool for tracing the biosynthetic origin of amino acid carbon skeletons, based on naturally occurring stable carbon isotope patterns in individual amino acids (δ13CAA). We focus on two important aspects for δ13CAA utility in sedimentary paleoarchives: first, the fidelity of source diagnostic of algal δ13CAA patterns across different oceanographic growth conditions, and second, the ability of δ13CAA patterns to record the degree of subsequent microbial amino acid synthesis after sedimentary burial. Using the marine diatom Thalassiosira weissflogii, we tested under controlled conditions how δ13CAA patterns respond to changing environmental conditions, including light, salinity, temperature, and pH. Our findings show that while differing oceanic growth conditions can change macromolecular cellular composition, δ13CAA isotopic patterns remain largely invariant. These results emphasize that δ13CAA patterns should accurately record biosynthetic sources across widely disparate oceanographic conditions. We also explored how δ13CAA patterns change as a function of age, total nitrogen and organic carbon content after burial, in a marine sediment core from a coastal upwelling area off Peru. Based on the four most informative amino acids for distinguishing between diatom and bacterial sources (i.e., isoleucine, lysine, leucine and tyrosine), bacterially derived amino acids ranged from 10 to 15 % in the sediment layers from the last 5000 years, and up to 35 % during the last glacial period. The greater bacterial contributions in older sediments indicate that bacterial activity and amino acid resynthesis progressed, approximately as a function of sediment age, to a substantially larger degree than suggested by changes in total organic nitrogen and carbon content. It is uncertain whether archaea may have contributed to sedimentary δ13CAA patterns we observe, and controlled culturing studies will be needed to investigate whether δ13CAA patterns can differentiate bacterial from archeal sources. Further research efforts are also needed to understand how closely δ13CAA patterns derived from hydrolyzable amino acids represent total sedimentary proteineincous material, and more broadly sedimentary organic nitrogen. Overall, however, both our culturing and sediment studies suggest that δ13CAA patterns in sediments will represent a novel proxy for understanding both primary production sources, and the direct bacterial role in the ultimate preservation of sedimentary organic matter.

Description: Upwelling is an important process, bringing gases and nutrients into the ocean mixed layer. The upwelling velocities, however, are too small to be measured directly. Here we use the surface disequilibrium of the 3He / 4He ratio measured in two coastal upwelling regions off Peru in the Pacific ocean and off Mauritania in the Atlantic ocean to calculate the regional distribution of vertical velocities. To also account for the fluxes by diapycnal mixing, microstructure-based observations of the vertical diffusivity have been performed on all four cruises analysed in this study. The upwelling velocities in the coastal regions vary between 1.1 ± 0.3 × 10−5 and 2.8 ± 1.5 × 10−5 m s−1 for all cruises. Vertical velocities are also inferred from the divergence of the wind-driven Ekman transport. In the coastal regimes, both methods agree within the error range. Further offshore, the helium-derived vertical velocity still reaches 1 × 10−5 m s−1, whereas the wind-driven upwelling from Ekman suction is smaller by up to 1 order of magnitude. One reason for this difference is ascribed to eddy-induced upwelling. Both advective and diffusive nutrient fluxes into the mixed layer are calculated based on the helium-derived vertical velocities and the vertical diffusivities. The advective part of these fluxes makes up at about 50 % of the total. The nutrient flux into the mixed layer in the coastal upwelling regimes is equivalent to a net community production (NCP) of 1.3 ± 0.3 g C m2 d−1 off Peru and 1.6–2.1 ± 0.5 g C m2 d−1 off Mauritania.

Description: Nitrogen (N) and phosphorus (P) availability, in addition to other macro- and micronutrients, determine the strength of the ocean's carbon (C) uptake, and variation in the N : P ratio of inorganic nutrient pools is key to phytoplankton growth. A similarity between C : N : P ratios in the plankton biomass and deep-water nutrients was observed by Alfred C. Redfield around 80 years ago and suggested that biological processes in the surface ocean controlled deep-ocean chemistry. Recent studies have emphasized the role of inorganic N : P ratios in governing biogeochemical processes, particularly the C : N : P ratio in suspended particulate organic matter (POM), with somewhat less attention given to exported POM and dissolved organic matter (DOM). Herein, we extend the discussion on ecosystem C : N : P stoichiometry but also examine temporal variation in stoichiometric relationships. We have analyzed elemental stoichiometry in the suspended POM and total (POM + DOM) organic-matter (TOM) pools in the upper 100 m and in the exported POM and subeuphotic zone (100–500 m) inorganic nutrient pools from the monthly data collected at the Bermuda Atlantic Time-series Study (BATS) site located in the western part of the North Atlantic Ocean. C : N and N : P ratios in TOM were at least twice those in the POM, while C : P ratios were up to 5 times higher in TOM compared to those in the POM. Observed C : N ratios in suspended POM were approximately equal to the canonical Redfield ratio (C : N : P = 106 : 16 : 1), while N : P and C : P ratios in the same pool were more than twice the Redfield ratio. Average N : P ratios in the subsurface inorganic nutrient pool were ~ 26 : 1, squarely between the suspended POM ratio and the Redfield ratio. We have further linked variation in elemental stoichiometry to that of phytoplankton cell abundance observed at the BATS site. Findings from this study suggest that elemental ratios vary with depth in the euphotic zone, mainly due to different growth rates of cyanobacterial cells. We have also examined the role of the Arctic Oscillation on temporal patterns in C : N : P stoichiometry. This study strengthens our understanding of the variability in elemental stoichiometry in different organic-matter pools and should improve biogeochemical models by constraining the range of non-Redfield stoichiometry and the net relative flow of elements between pools.

Description: The eastern tropical North Atlantic (ETNA) is characterized by a highly productive coastal upwelling system and a moderate oxygen minimum zone with lowest open ocean oxygen (O2) concentrations of around 40 μmol kg−1. Only recently, the discovery of re-occurring mesoscale eddies with sometimes close to anoxic O2 concentrations (〈1 μmol kg−1) and located just below the mixed layer challenged our understanding of O2 distribution and biogeochemical processes in this area. Here, we present the first metagenomic dataset from a deoxygenated anticyclonic modewater eddy in the open waters of the ETNA. In the eddy, we observed a significantly lower bacterial diversity compared to surrounding waters, along with a significant community shift. We detected enhanced primary productivity in the surface layer of the eddy indicated by elevated chlorophyll concentrations and increased carbon uptake rates up to three times as high as in surrounding waters. Carbon uptake below the euphotic zone correlated to the presence of a specific high-light ecotype of Prochlorococcus, which is usually underrepresented in the ETNA. Our combined data indicate that high primary production in the eddy fuels export production and the presence of a specific microbial community responsible for enhanced respiration at shallow depths, below the mixed layer base. Progressively decreasing O2 concentrations in the eddy were found to promote transcription of the key gene for denitrification, nirS, in the O2-depleted core waters. This process is usually absent from the open ETNA waters. In the light of future ocean deoxygenation our results show exemplarily that even distinct events of anoxia have the potential to alter microbial community structures and with that critically impact primary productivity and biogeochemical processes of oceanic water bodies.

Description: Results from measurements of wave slope statistics during the R/V Meteor M91 cruise in the coastal upwelling regions off the coast of Peru are reported. Wave slope probability distributions were measured with an instrument based on the reflection of light at the water surface and a method very similar to the Cox and Munk (1954b) sun glitter technique. During the cruise, the mean square slope (mss) of the waves was found to be very variable, despite the limited range of encountered wind speeds. The Cox and Munk (1954b) parameterization for clean water is found to overestimate mss, but most measurements fall in the range spanned by their clean water and slick parameterizations. The observed variability of mss is attributed to the wave damping effect of surface films, generated by increased biological production in the upwelling zones. The small footprint and high temporal resolution of the measurement allows for tracking abrupt changes in conditions caused by the often patchy structure of the surface films.

Description: In recent updates of the HITRAN water vapour H2O spectroscopic compilation covering the blue spectral region (here: 394–480 nm) significant changes for the absorption bands at 416 and 426 nm were reported. In order to investigate the consistency of the different cross-sections calculated from these compilations, H2O vapour column density ratios for different spectral intervals were retrieved from long-path and multi-axis differential optical absorption spectroscopy (DOAS) measurements. We observed a significant improvement of the DOAS evaluation when using the updated HITRAN water vapour absorption cross-sections for the calculation of the reference spectra. In particular the magnitudes of the residual spectra as well as the fit errors were reduced. However, we also found that the best match between measurement and model is reached when the absorption cross-section of groups of lines are scaled by factors ranging from 0.5 to 1.9, suggesting that the HITRAN water vapour absorption compilation still needs significant corrections. For this spectral region we present correction factors for HITRAN 2009, HITRAN 2012, HITEMP and BT2 derived from field measurements. Additionally, upper limits for water vapour absorption in the UV-A range from 330 to 390 nm are given.

Description: In a changing climate, marine pelagic biogeochemistry may modulate the atmospheric concentrations of climate-relevant species such as CO2 and N2O. To date, projections rely on earth system models, featuring simple pelagic biogeochemical model components, embedded into 3-D ocean circulation models. Most of these biogeochemical model components rely on the hyperbolic Michaelis–Menten (MM) formulation which specifies the limiting effect of light and nutrients on carbon assimilation by autotrophic phytoplankton. The respective MM constants, along with other model parameters, of 3-D coupled biogeochemical ocean-circulation models are usually tuned; the parameters are changed until a "reasonable" similarity to observed standing stocks is achieved. Here, we explore with twin experiments (or synthetic "observations") the demands on observations that allow for a more objective estimation of model parameters. We start with parameter retrieval experiments based on "perfect" (synthetic) observations which we distort, step by step, by low-frequency noise to approach realistic conditions. Finally, we confirm our findings with real-world observations. In summary, we find that MM constants are especially hard to constrain because even modest noise (10 %) inherent to observations may hinder the parameter retrieval already. This is of concern since the MM parameters are key to the model's sensitivity to anticipated changes in the external conditions. Furthermore, we illustrate problems caused by high-order parameter dependencies when parameter estimation is based on sparse observations of standing stocks. Somewhat counter to intuition, we find that more observational data can sometimes degrade the ability to constrain certain parameters.

Description: Air-sea dimethylsulfide (DMS) fluxes and bulk air-sea gradients were measured over the Southern Ocean in February-March 2012 during the Surface Ocean Aerosol Production (SOAP) study. The cruise encountered three distinct phytoplankton bloom regions, consisting of two blooms with moderate DMS levels, and a high biomass, dinoflagellate-dominated bloom with high seawater DMS levels (〉 15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m s-1. Bin averaging the data resulted in a linear relationship between wind speed and mean gas transfer velocity consistent with that previously observed. However, the wind-speed-binned gas transfer data distribution at all wind speeds is positively skewed. The flux and seawater DMS distributions were also positively skewed, which suggests that eddy covariance-derived gas transfer velocities are consistently influenced by additional, log-normal noise. A flux footprint analysis was conducted during a transect into the prevailing wind and through elevated DMS levels in the dinoflagellate bloom. Accounting for the temporal/spatial separation between flux and seawater concentration significantly reduces the scatter in computed transfer velocity. The SOAP gas transfer velocity data show no obvious modification of the gas transfer-wind speed relationship by biological activity or waves. This study highlights the challenges associated with eddy covariance gas transfer measurements in biologically active and heterogeneous bloom environments.

Description: Global models of the oceanic nitrogen cycle are subject to many uncertainties, among them type and form of biogeochemical processes involved in the fixed nitrogen cycle, and the spatial and temporal scales, on which the global nitrogen budget is regulated. We investigate these aspects using a global model of ocean biogeochemistry, that explicitly considers phosphorus and nitrogen, including pelagic denitrification and nitrogen fixation as sink and source terms of fixed nitrogen, respectively. The model explores different parameterizations of organic matter sinking speed, oxidant affinity of oxic and suboxic remineralization, and regulation of nitrogen fixation by temperature and different stoichiometric ratios. Examination of the initial transient behaviour of different model setups initialized from observed tracer distributions reveal changes in simulated nitrogen inventories and fluxes particularly during the first centuries. Millennial timescales have to be resolved in order to bring all biogeochemical and physical processes into a dynamically consistent steady state, for which global patterns of biogeochemical tracers and fluxes are reproduced quite well. Analysis of global properties suggests that particularly particle sinking speed, but also the parameterization of denitrification determines the extent of oxygen minimum zones, global nitrogen fluxes, and hence the oceanic nitrogen inventory. However, the ways and directions, in which different parameterizations of particle sinking, nitrogen fixation and denitrification affect the global diagnostics, are different, suggesting that these may, in principle, be constrained independently from each other. Analysis of the model misfit suggests a particle flux profile close to the one suggested by Martin et al. (1987). Simulated pelagic denitrification best agrees with the lower values between 59 and 84 Tg N yr−1 recently estimated by other authors.

Description: In remote sensing applications, such as differential optical absorption spectroscopy (DOAS), atmospheric scattering processes need to be considered. After inelastic scattering on N2 and O2 molecules, the scattered photons occur as additional intensity at a different wavelength, effectively leading to filling-in of both solar Fraunhofer lines and absorptions of atmospheric constituents. Measured spectra in passive DOAS applications are typically corrected for rotational Raman scattering (RRS), also called Ring effect, which represents the main contribution to inelastic scattering. In contrast to that, vibrational Raman scattering (VRS) of N2 and O2 has often been thought to be negligible, but also contributes. Consequences of VRS are red-shifted Fraunhofer structures in scattered light spectra and filling-in of Fraunhofer lines, additional to RRS. We describe how to calculate VRS correction spectra in analogy to the Ring spectrum. We discuss further the impact of VRS cross-sections for O2 and N2 on passive DOAS measurements. The relevance of VRS is shown for the first time in spectral evaluations of Multi-Axis DOAS data. This measurement data yields in agreement with calculated scattering cross-sections, that the observed VRS cross-section amounts to 2.2 ± 0.4% of the cross-section of RRS under tropospheric conditions. It is concluded, that this phenomenon has to be included in the spectral evaluation of weak absorbers as it reduces the measurement error significantly and can cause apparent differential optical depth of up to 2.5 × 10−4. Its influence on the spectral retrieval of IO, Glyoxal, water vapour and NO2 in the blue wavelength range is evaluated. For measurements with a large Ring signal a significant and systematic bias of NO2 dSCDs up to (−3.8 ± 0.4) × 1014 molec cm−2 at low elevation angles is observed if this effect is not considered.

Description: It has been speculated that macrophytes beds might act as a refuge for calcifiers from ocean acidification. In the shallow nearshores of the western Kiel Bay (Baltic Sea), mussel and seagrass beds are interlacing, forming a mosaic habitat. Naturally, the diverse physiological activities of seagrasses and mussels are affected by seawater carbonate chemistry and they locally modify it in return. Calcification by shellfishes is sensitive to seawater acidity; therefore the photosynthetic activity of seagrasses in confined shallow waters creates favorable chemical conditions to calcification at daytime but turn the habitat less favorable or even corrosive to shells at night. In contrast, mussel respiration releases CO2, turning the environment more favorable for photosynthesis by adjacent seagrasses. At the end of summer, these dynamics are altered by the invasion of high pCO2/low O2 coming from the deep water of the Bay. However, it is in summer that mussel spats settle on the leaves of seagrasses until migrating to the permanent habitat where they will grow adult. These early life phases (larvae/spats) are considered as most sensitive with regard to seawater acidity. So far, the dynamics of CO2 have never been continuously measured during this key period of the year, mostly due to the technological limitations. In this project we used a combination of state-of-the-art technologies and discrete sampling to obtain high-resolution time-series of pCO2 and O2 at the interface between a seagrass and a mussel patch in Kiel Bay in August and September 2013. From these, we derive the entire carbonate chemistry using statistical models. We found the monthly average pCO2 more than 50 % (approx. 640 μatm for August and September) above atmospheric equilibrium right above the mussel patch together with large diel variations of pCO2 within 24 h: 887 ± 331 μatm in August and 742 ± 281 μatm in September (mean ± SD). We observed important daily corrosiveness for calcium carbonates (Ωarag and Ωcalc 〈 1) centered on sunrise. On the positive side, the investigated habitat never suffered from hypoxia during the study period. We emphasize the need for more experiments on the impact of these acidic conditions on (juvenile) mussels with a focus on the distinct day-night variations observed.

Description: We report on data from an oceanographic cruise in the Mediterranean Sea on the German research vessel Poseidon in April 2014. Data were taken on a west–east section, starting at the Strait of Gibraltar and ending south-east of Crete, as well on sections in the Ionian and Adriatic Sea. The objectives of the cruise were threefold: to contribute to the investigation of the spatial evolution of the Levantine Intermediate Water (LIW) properties and of the deep water masses in the eastern Mediterranean Sea, and to investigate the mesoscale variability of the upper water column. The measurements include salinity, temperature, oxygen and currents and were conducted with a conductivity, temperature and depth(CTD)/rosette system, an underway CTD and an acoustic Doppler current profiler (ADCP). The sections are on tracks which have been sampled during several other cruises, thus supporting the opportunity to investigate the long-term temporal development of the different variables. The use of an underway CTD made it possible to conduct measurements of temperature and salinity with a high horizontal spacing of 6 nm between stations and a vertical spacing of 1 dbar for the upper 800 m of the water column.

Description: This numerical study provides the first simulation of the anthropogenic tritium invasion and its decay product helium-3 (He-3) in the Mediterranean Sea. The simulation covers the entire tritium (H-3) transient generated by the atmospheric nuclear weapons tests performed in the 1950s and early 1960s and is run till 2011. Tritium, helium-3 and their derived age estimates are particularly suitable for studying intermediate and deep-water ventilation and spreading of water masses at intermediate/deep levels. The simulation is made using a high-resolution regional model NEMO (Nucleus for European Modelling of the Ocean), in a regional configuration for the Mediterranean Sea called MED12, forced at the surface with prescribed tritium evolution derived from observations. The simulation is compared to measurements of tritium and helium-3 performed along large-scale transects in the Mediterranean Sea during the last few decades on cruises of R/V Meteor: M5/6, M31/1, M44/4, M51/2, M84/3, and R/V Poseidon: 234. The results show that the input function used for the tritium generates a realistic distribution of the main hydrographic features of the Mediterranean Sea circulation. In the eastern basin, the results highlight the weak formation of Adriatic Deep Water in the model, which explains its weak contribution to the Eastern Mediterranean Deep Water (EMDW) in the Ionian sub-basin. It produces a realistic representation of the Eastern Mediterranean Transient (EMT) signal, simulating a deep-water formation in the Aegean subbasin at the beginning of 1993, with a realistic timing of deep-water renewal in the eastern basin.

Description: Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates as well as consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuels and industry (EFF) are based on energy statistics and cement production data, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover change (some including nitrogen–carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2005–2014), EFF was 9.0 ± 0.5 GtC yr−1, ELUC was 0.9 ± 0.5 GtC yr−1, GATM was 4.4 ± 0.1 GtC yr−1, SOCEAN was 2.6 ± 0.5 GtC yr−1, and SLAND was 3.0 ± 0.8 GtC yr−1. For the year 2014 alone, EFF grew to 9.8 ± 0.5 GtC yr−1, 0.6 % above 2013, continuing the growth trend in these emissions, albeit at a slower rate compared to the average growth of 2.2 % yr−1 that took place during 2005–2014. Also, for 2014, ELUC was 1.1 ± 0.5 GtC yr−1, GATM was 3.9 ± 0.2 GtC yr−1, SOCEAN was 2.9 ± 0.5 GtC yr−1, and SLAND was 4.1 ± 0.9 GtC yr−1. GATM was lower in 2014 compared to the past decade (2005–2014), reflecting a larger SLAND for that year. The global atmospheric CO2 concentration reached 397.15 ± 0.10 ppm averaged over 2014. For 2015, preliminary data indicate that the growth in EFF will be near or slightly below zero, with a projection of −0.6 [range of −1.6 to +0.5] %, based on national emissions projections for China and the USA, and projections of gross domestic product corrected for recent changes in the carbon intensity of the global economy for the rest of the world. From this projection of EFF and assumed constant ELUC for 2015, cumulative emissions of CO2 will reach about 555 ± 55 GtC (2035 ± 205 GtCO2) for 1870–2015, about 75 % from EFF and 25 % from ELUC. This living data update documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this data set (Le Quéré et al., 2015, 2014, 2013). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP_2015).

Description: The presence of melt ponds on the Arctic sea ice strongly affects the energy balance of the Arctic Ocean in summer. It affects albedo as well as transmittance through the sea ice, which has consequences for the heat balance and mass balance of sea ice. An algorithm to retrieve melt pond fraction and sea ice albedo from Medium Resolution Imaging Spectrometer (MERIS) data is validated against aerial, shipborne and in situ campaign data. The results show the best correlation for landfast and multiyear ice of high ice concentrations. For broadband albedo, R2 is equal to 0.85, with the RMS (root mean square) being equal to 0.068; for the melt pond fraction, R2 is equal to 0.36, with the RMS being equal to 0.065. The correlation for lower ice concentrations, subpixel ice floes, blue ice and wet ice is lower due to ice drift and challenging for the retrieval surface conditions. Combining all aerial observations gives a mean albedo RMS of 0.089 and a mean melt pond fraction RMS of 0.22. The in situ melt pond fraction correlation is R2 = 0.52 with an RMS = 0.14. Ship cruise data might be affected by documentation of varying accuracy within the Antarctic Sea Ice Processes and Climate (ASPeCt) protocol, which may contribute to the discrepancy between the satellite value and the observed value: mean R2 = 0.044, mean RMS = 0.16. An additional dynamic spatial cloud filter for MERIS over snow and ice has been developed to assist with the validation on swath data.

Description: Large-scale fully coupled Earth system models (ESMs) are usually applied in climate projections like the IPCC (Intergovernmental Panel on Climate Change) reports. In these models internal variability is often within the correct order of magnitude compared with the observed climate, but due to internal variability and arbitrary initial conditions they are not able to reproduce the observed timing of climate events or shifts as for instance observed in the El Niño–Southern Oscillation (ENSO), the Pacific Decadal Oscillation (PDO), or the Atlantic Meridional Overturning Circulation (AMOC). Additional information about the real climate history is necessary to constrain ESMs; not only to emulate the past climate, but also to introduce a potential forecast skill into these models through a proper initialisation. We attempt to do this by extending the fully coupled climate model Max Planck Institute Earth System Model (MPI-ESM) using a partial coupling technique (Modini-MPI-ESM). This method is implemented by adding reanalysis wind-field anomalies to the MPI-ESM's inherent climatological wind field when computing the surface wind stress that is used to drive the ocean and sea ice model. Using anomalies instead of the full wind field reduces potential model drifts, because of different mean climate states of the unconstrained MPI-ESM and the partially coupled Modini-MPI-ESM, that could arise if total observed wind stress was used. We apply two different reanalysis wind products (National Centers for Environmental Prediction, Climate Forecast System Reanalysis (NCEPcsfr) and ERA-Interim reanalysis (ERAI)) and analyse the skill of Modini-MPI-ESM with respect to several observed oceanic, atmospheric, and sea ice indices. We demonstrate that Modini-MPI-ESM has a significant skill over the time period 1980–2013 in reproducing historical climate fluctuations, indicating the potential of the method for initialising seasonal to decadal forecasts. Additionally, our comparison of the results achieved with the two reanalysis wind products NCEPcsfr and ERAI indicates that in general applying NCEPcsfr results in a better reconstruction of climate variability since 1980.

Description: Marine organisms precipitate 0.5–2.0 Gt of carbon as calcium carbonate (CaCO3) every year with a profound impact on global biogeochemical element cycles. Biotic calcification relies on calcium ions (Ca2+) and generally on bicarbonate ions (HCO3−) as CaCO3 substrates and can be inhibited by high proton (H+) concentrations. The seawater concentration of carbonate ions (CO32−) and the CO32−-dependent CaCO3 saturation state (ΩCaCO3) seem to be irrelevant in this production process. Nevertheless, calcification rates and the success of calcifying organisms in the oceans often correlate surprisingly well with these two carbonate system parameters. This study addresses this dilemma through rearrangement of carbonate system equations which revealed an important proportionality between [CO32−] or ΩCaCO3 and the ratio of [HCO3−] to [H+]. Due to this proportionality, calcification rates will always correlate equally well with [HCO3−]/[H+] as with [CO32−] or ΩCaCO3 when temperature, salinity, and pressure are constant. Hence, [CO32−] and ΩCaCO3 may simply be very good proxies for the control by [HCO3−]/[H+] where [HCO3−] would be the inorganic carbon substrate and [H+] would function as calcification inhibitor. If the "substrate-inhibitor ratio" (i.e. [HCO3−]/[H+]) rather than [CO32−] or ΩCaCO3 controls CaCO3 formation then some of the most common paradigms in ocean acidification research need to be reviewed. For example, the absence of a latitudinal gradient in [HCO3−]/[H+] in contrast to [CO32−] and ΩCaCO3 could modify the common assumption that high latitudes are affected most severely by ocean acidification.

Description: In open-ocean regions, as is the Eastern Tropical North Atlantic (ETNA), pelagic production is the main source of dissolved organic matter (DOM) and is affected by dissolved inorganic nitrogen (DIN) and phosphorus (DIP) concentrations. Changes in pelagic production under nutrient amendments were shown to also modify DOM quantity and quality. However, little information is available about the effects of nutrient variability on chromophoric (CDOM) and fluorescent (FDOM) DOM dynamics. Here we present results from two mesocosm experiments ("Varied P" and "Varied N") conducted with a natural plankton community from the ETNA, where the effects of DIP and DIN supply on DOM optical properties were studied. CDOM accumulated proportionally to phytoplankton biomass during the experiments. Spectral slope (S) decreased over time indicating accumulation of high molecular weight DOM. In Varied N, an additional CDOM portion, as a result of bacterial DOM reworking, was determined. It increased the CDOM fraction in DOC proportionally to the supplied DIN. The humic-like FDOM component (Comp.1) was produced by bacteria proportionally to DIN supply. The protein-like FDOM component (Comp.2) was released irrespectively to phytoplankton or bacterial biomass, but depended on DIP and DIN concentrations. Under high DIN supply, Comp.2 was removed by bacterial reworking, leading to an accumulation of humic-like Comp.1. No influence of nutrient availability on amino acid-like FDOM component in peptide form (Comp.3) was observed. Comp.3 potentially acted as an intermediate product during formation or degradation of Comp.2. Our findings suggest that changes in nutrient concentrations may lead to substantial responses in the quantity and quality of optically active DOM and, therefore, might bias results of the applied in situ optical techniques for an estimation of DOC concentrations in open-ocean regions.

Description: At present, anthropogenic halogens and oceanic emissions of Very Short-Lived Substances (VSLS) are responsible for stratospheric ozone destruction. Emissions of the, mostly long-lived, anthropogenic halogens have been reduced, and as a consequence, their atmospheric abundance has started to decline since the beginning of the 21st century. Emissions of VSLS are, on the other hand, expected to increase in the future. VSLS are known to have large natural sources; however increasing evidence arises that their oceanic production and emission is enhanced by anthropogenic activities. Here, we introduce a new approach of assessing the overall impact of all oceanic halogen emissions on stratospheric ozone by calculating Ozone Depletion Potential (ODP)-weighted emissions of VSLS. Seasonally and spatially dependent, global distributions are derived exemplary for CHBr3 for the period 1999–2006. At present, ODP-weighted emissions of CHBr3 amount up to 50% of ODP-weighted anthropogenic emissions of CFC-11 and to 9% of all long-lived ozone depleting substances. The ODP-weighted emissions are large where strong oceanic emissions coincide with high-reaching convective activity and show pronounced peaks at the equator and the coasts with largest contributions from the Maritime Continent and West Pacific. Variations of tropical convective activity lead to seasonal shifts in the spatial distribution of the ODP with the updraught mass flux explaining 71% of the variance of the ODP distribution. Future climate projections based on RCP8.5 scenario suggest a 31% increase of the ODP-weighted CHBr3 emissions until 2100 compared to present values. This increase is related to larger convective activity and increasing emissions in a future climate; however, is reduced at the same time by less effective bromine-related ozone depletion. The comparison of the ODP-weighted emissions of short and long-lived halocarbons provides a new concept for assessing the overall impact of oceanic bromine emissions on stratospheric ozone depletion for current conditions and future projections.

Description: Temperature, salinity and oxygen data collected during April and June 2011 (M84/3 and P414 cruises respectively) are analysed to derive the oceanographic characteristics of the Eastern Mediterranean (EM) basin. These observed characteristics are compared with those from previous cruises over the period 1987–2011. As a result, the interannual and decadal variability of the EM thermohaline properties are discussed in the context of the evolution of the Eastern Mediterranean Transient (EMT) and of the general circulation of the basin. We found that the state of the EM is still far from the pre-EMT conditions, though the 2011 results possibly indicate a slow return to this status. In particular, a comparison between thermohaline property evolution deriving from interannual variability of the preconditioning and air–sea interaction (heat fluxes) in the South Adriatic and the Cretan Seas reveals aspects of the alternation of the two dense water sources (Adriatic and Aegean) during the last three decades, which have strong implications for the hydrographic characteristics of the intermediate and deep layers of the Ionian and Levantine basins.

Description: The shrinking Arctic sea ice cover observed during the last decades is probably the clearest manifestation of ongoing climate change. While climate models in general reproduce the sea ice retreat in the Arctic during the 20th century and simulate further sea ice area loss during the 21st century in response to anthropogenic forcing, the models suffer from large biases and the model results exhibit considerable spread. The last generation of climate models from World Climate Research Programme Coupled Model Intercomparison Project Phase 5 (CMIP5), when compared to the previous CMIP3 model ensemble and considering the whole Arctic, were found to be more consistent with the observed changes in sea ice extent during the recent decades. Some CMIP5 models project strongly accelerated (non-linear) sea ice loss during the first half of the 21st century. Here, complementary to previous studies, we compare results from CMIP3 and CMIP5 with respect to regional Arctic sea ice change. We focus on September and March sea ice. Sea ice area (SIA) variability, sea ice concentration (SIC) variability, and characteristics of the SIA seasonal cycle and interannual variability have been analysed for the whole Arctic, termed Entire Arctic, Central Arctic and Barents Sea. Further, the sensitivity of SIA changes to changes in Northern Hemisphere (NH) averaged temperature is investigated and several important dynamical links between SIA and natural climate variability involving the Atlantic Meridional Overturning Circulation (AMOC), North Atlantic Oscillation (NAO) and sea level pressure gradient (SLPG) in the western Barents Sea opening serving as an index of oceanic inflow to the Barents Sea are studied. The CMIP3 and CMIP5 models not only simulate a coherent decline of the Arctic SIA but also depict consistent changes in the SIA seasonal cycle and in the aforementioned dynamical links. The spatial patterns of SIC variability improve in the CMIP5 ensemble, particularly in summer. Both CMIP ensembles depict a significant link between the SIA and NH temperature changes. Our analysis suggests that, on average, the sensitivity of SIA to external forcing is enhanced in the CMIP5 models. The Arctic SIA variability response to anthropogenic forcing is different in CMIP3 and CMIP5. While the CMIP3 models simulate increased variability in March and September, the CMIP5 ensemble shows the opposite tendency. A noticeable improvement in the simulation of summer SIA by the CMIP5 models is often accompanied by worse results for winter SIA characteristics. The relation between SIA and mean AMOC changes is opposite in September and March, with March SIA changes being positively correlated with AMOC slowing. Finally, both CMIP ensembles demonstrate an ability to capture, at least qualitatively, important dynamical links of SIA to decadal variability of the AMOC, NAO and SLPG. SIA in the Barents Sea is strongly overestimated by the majority of the CMIP3 and CMIP5 models, and projected SIA changes are characterized by a large spread giving rise to high uncertainty.

Description: Changes in fire activity over the last 8000 years are simulated with a global fire model driven by changes in climate and vegetation cover. The changes were separated into those caused through variations in fuel availability, fuel moisture or wind speed, which react differently to changes in climate. Disentangling these controlling factors helps in understanding the overall climate control on fire activity over the Holocene. Globally the burned area is simulated to increase by 2.5% between 8000 and 200 cal yr BP, with larger regional changes compensating nearly evening out on a global scale. Despite the absence of anthropogenic fire ignitions, the simulated trends in fire activity agree reasonably well with continental-scale reconstructions from charcoal records, with the exception of Europe. For some regions the change in fire activity is predominantly controlled through changes in fuel availability (Australia monsoon, Central America tropics/subtropics). For other regions changes in fuel moisture are more important for the overall trend in fire activity (North America, Sub-Saharan Africa, Europe, Asia monsoon). In Sub-Saharan Africa, for example, changes in fuel moisture alone lead to an increase in fire activity between 8000 and 200 cal yr BP, while changes in fuel availability lead to a decrease. Overall, the fuel moisture control is dominating the simulated fire activity for Sub-Saharan Africa. The simulations clearly demonstrate that both changes in fuel availability and changes in fuel moisture are important drivers for the fire activity over the Holocene. Fuel availability and fuel moisture do, however, have different climate controls. As such, observed changes in fire activity cannot be related to single climate parameters such as precipitation or temperature alone. Fire models, as applied in this study, in combination with observational records can help in understanding the climate control on fire activity, which is essential to project future fire activity.

Description: Spatial and temporal characteristics of the Storfjorden polynya, which forms regularly in the proximity of the islands Spitsbergen, Barentsøya and Edgeøya in the Svalbard archipelago under the influence of strong north-easterly winds, have been investigated for the period 2002/2003 to 2013/2014 using thermal infrared satellite imagery. Thin-ice thicknesses were calculated from MODIS ice-surface temperatures, combined with ECMWF ERA-Interim atmospheric reanalysis data in an energy-balance model. Based on calculated thin-ice thicknesses, associated quantities like polynya area and total ice production were derived and compared to previous remote sensing and modeling studies. A basic coverage-correction scheme was applied to account for cloud-gaps in the daily composites. The sea ice in the Storfjorden area experiences a late fall freeze-up in several years over the 12 winter-period, with an increasing frequency of large polynya events until the end of December. During the regarded period, the mean polynya area is 4555.7 ± 1542.9 km2. The average ice production in the fjord is estimated with 28.3 ± 8.5 km3 per winter and therefore lower than in previous studies. Despite this comparatively short record of 12 winter-seasons, a significant positive trend of 20.2 km3 per decade could be detected, which contrasts earlier reports of a slightly negative trend in accumulated ice production prior to 2002. Derived estimates underline the importance of this relatively small coastal polynya system considering its contribution to the cold halocline layer through salt release during ice formation processes.

Description: Bivalve calcification, particularly of the early larval stages, is highly sensitive to the change in ocean carbonate chemistry resulting from atmospheric CO2 uptake. Earlier studies suggested that declining seawater [CO32−] and thereby lowered carbonate saturation affect shell production. However, disturbances of physiological processes such as acid-base regulation by adverse seawater pCO2 and pH can affect calcification in a secondary fashion. In order to determine the exact carbonate system component by which growth and calcification are affected it is necessary to utilize more complex carbonate chemistry manipulations. As single factors, pCO2 had no effects and [HCO3-] and pH had only limited effects on shell growth, while lowered [CO32−] strongly impacted calcification. Dissolved inorganic carbon (CT) limiting conditions led to strong reductions in calcification, despite high [CO32−], indicating that [HCO3-] rather than [CO32−] is the inorganic carbon source utilized for calcification by mytilid mussels. However, as the ratio [HCO3-] / [H+] is linearly correlated with [CO32−] it is not possible to differentiate between these under natural seawater conditions. An equivalent of about 80 μmol kg−1 [CO32−] is required to saturate inorganic carbon supply for calcification in bivalves. Below this threshold biomineralization rates rapidly decline. A comparison of literature data available for larvae and juvenile mussels and oysters originating from habitats differing substantially with respect to prevailing carbonate chemistry conditions revealed similar response curves. This suggests that the mechanisms which determine sensitivity of calcification in this group are highly conserved. The higher sensitivity of larval calcification seems to primarily result from the much higher relative calcification rates in early life stages. In order to reveal and understand the mechanisms that limit or facilitate adaptation to future ocean acidification, it is necessary to better understand the physiological processes and their underlying genetics that govern inorganic carbon assimilation for calcification.

Description: Mechanisms governing phosphorus (P) speciation in coastal sediments remain largely unknown due to the diversity of coastal environments and poor analytical specificity for P phases. We investigated P speciation across salinity gradients comprising diverse ecosystems in a P-enriched estuary. To determine P load effects on P speciation we compared the high P site with a low P site. Octacalcium phosphate (OCP), authigenic apatite (carbonate fluorapatite, CFAP) and detrital apatite (fluorapatite) were quantitated in addition to Al/Fe-bound P (Al/Fe-P) and Ca-bound P (Ca-P). Gradients in sediment pH strongly affected P fractions across ecosystems and independent of the site-specific total P status. We found a pronounced switch from adsorbed Al/Fe-P to mineral Ca-P with decreasing acidity from land to sea. This switch occurred at near-neutral sediment pH and has possibly been enhanced by redox-driven phosphate desorption from iron oxyhydroxides. The seaward decline in Al/Fe-P was counterbalanced by the precipitation of Ca-P. Correspondingly, two location-dependent accumulation mechanisms occurred at the high P site due to the switch, leading to elevated Al/Fe-P at pH 〈 6.6 (landward; adsorption) and elevated Ca-P at pH 〉 6.6 (seaward; precipitation). Enhanced Ca-P precipitation by increased P loads was also evident from disproportional accumulation of metastable Ca-P (Ca-Pmeta) at the high P site. Here, sediments contained on average 6-fold higher Ca-Pmeta levels compared with the low P site, although these sediments contained only 2-fold more total Ca-P than the low P sediments. Phosphorus species distributions indicated that these elevated Ca-Pmeta levels resulted from transformation of fertilizer-derived Al/Fe-P to OCP and CFAP in nearshore areas. Formation of CFAP as well as its precursor, OCP, results in P retention in coastal zones and can thus lead to substantial inorganic P accumulation in response to anthropogenic P input.

Description: Present day oceans are well ventilated, with the exception of mid-depth oxygen minimum zones (OMZs) under high surface water productivity, regions of sluggish circulation, and restricted marginal basins. In the Mesozoic, however, entire oceanic basins transiently became dysoxic or anoxic. The Cretaceous ocean anoxic events (OAEs) were characterised by laminated organic-carbon rich shales and low-oxygen indicating trace fossils preserved in the sedimentary record. Yet assessments of the intensity and extent of Cretaceous near-bottom water oxygenation have been hampered by deep or long-term diagenesis and the evolution of marine biota serving as oxygen indicators in today's ocean. Sedimentary features similar to those found in Cretaceous strata were observed in deposits underlying Recent OMZs, where bottom-water oxygen levels, the flux of organic matter, and benthic life have been studied thoroughly. Their implications for constraining past bottom-water oxygenation are addressed in this review. We compared OMZ sediments from the Peruvian upwelling with deposits of the late Cenomanian OAE 2 from the north-west African shelf. Holocene laminated sediments are encountered at bottom-water oxygen levels of 〈 7 μmol kg−1 under the Peruvian upwelling and 〈 5 μmol kg−1 in California Borderland basins and the Pakistan Margin. Seasonal to decadal changes of sediment input are necessary to create laminae of different composition. However, bottom currents may shape similar textures that are difficult to discern from primary seasonal laminae. The millimetre-sized trace fossil Chondrites was commonly found in Cretaceous strata and Recent oxygen-depleted environments where its diameter increased with oxygen levels from 5 to 45 μmol kg−1. Chondrites has not been reported in Peruvian sediments but centimetre-sized crab burrows appeared around 10 μmol kg−1, which may indicate a minimum oxygen value for bioturbated Cretaceous strata. Organic carbon accumulation rates ranged from 0.7 and 2.8 g C cm−2 kyr−1 in laminated OAE 2 sections in Tarfaya Basin, Morocco, matching late Holocene accumulation rates of laminated Peruvian sediments under Recent oxygen levels below 5 μmol kg−1. Sediments deposited at 〉 10 μmol kg−1 showed an inverse exponential relationship of bottom-water oxygen levels and organic carbon accumulation depicting enhanced bioirrigation and decomposition of organic matter with increased oxygen supply. In the absence of seasonal laminations and under conditions of low burial diagenesis, this relationship may facilitate quantitative estimates of palaeo-oxygenation. Similarities and differences between Cretaceous OAEs and late Quaternary OMZs have to be further explored to improve our understanding of sedimentary systems under hypoxic conditions.

Description: Gel particles such as the polysaccharidic transparent exopolymer particles (TEP) and the proteinaceous Coomassie stainable particles (CSP) play an important role in marine biogeochemical and ecological processes like particle aggregation and export, or microbial nutrition and growth. So far, effects of nutrient availability or of changes in nutrient ratios on gel particle production and fate are not well understood. The tropical ocean includes large oxygen minimum zones, where nitrogen losses due to anaerobic microbial activity result in a lower supply of nitrate relative to phosphate to the euphotic zone. Here, we report of two series of mesocosm experiments that were conducted with natural plankton communities collected from the eastern tropical North Atlantic (ETNA) close to Cape Verde in October 2012. The experiments were performed to investigate how different phosphate (experiment 1, Varied P: 0.15–1.58 μmol L−1) or nitrate (experiment 2, Varied N: 1.9–21.9 μmol L−1) concentrations affect the abundance and size distribution of TEP and CSP. In the days until the bloom peak was reached, a positive correlation between gel particle abundance and Chl a concentration was determined, linking the release of dissolved gel precursors and the subsequent formation of gel particles to autotrophic production. After the bloom peak, gel particle abundance remained stable or even increased, implying a continued partitioning of dissolved into particulate organic matter after biomass production itself ceased. During both experiments, differences between TEP and CSP dynamics were observed; TEP were generally more abundant than CSP. Changes in size distribution indicated aggregation of TEP after the bloom, while newly formed CSP decomposed. Abundance of gel particles clearly increased with nitrate concentration during the second experiment, suggesting that changes in [DIN] : [DIP] ratios can affect gel particle formation with potential consequences for carbon and nitrogen cycling as well as food web dynamics in tropical ecosystems.

Description: Marine phytoplankton have developed the remarkable ability to tightly regulate the concentration of free calcium ions in the intracellular cytosol at a level of ~ 0.1 μmol L−1 in the presence of seawater Ca2+ concentrations of 10 mmol L−1. The low cytosolic calcium ion concentration is of utmost importance for proper cell signalling function. While the regulatory mechanisms responsible for the tight control of intracellular Ca2+ concentration are not completely understood, phytoplankton taxonomic groups appear to have evolved different strategies, which may affect their ability to cope with changes in seawater Ca2+ concentrations in their environment on geological timescales. For example, the Cretaceous (145 to 66 Ma), an era known for the high abundance of coccolithophores and the production of enormous calcium carbonate deposits, exhibited seawater calcium concentrations up to 4 times present-day levels. We show that calcifying coccolithophore species (Emiliania huxleyi, Gephyrocapsa oceanica and Coccolithus braarudii) are able to maintain their relative fitness (in terms of growth rate and photosynthesis) at simulated Cretaceous seawater calcium concentrations, whereas these rates are severely reduced under these conditions in some non-calcareous phytoplankton species (Chaetoceros sp., Ceratoneis closterium and Heterosigma akashiwo). Most notably, this also applies to a non-calcifying strain of E. huxleyi which displays a calcium sensitivity similar to the non-calcareous species. We hypothesize that the process of calcification in coccolithophores provides an efficient mechanism to alleviate cellular calcium poisoning and thereby offered a potential key evolutionary advantage, responsible for the proliferation of coccolithophores during times of high seawater calcium concentrations. The exact function of calcification and the reason behind the highly ornate physical structures of coccoliths remain elusive.

Description: Trace element deposition from desert dust has important impacts on ocean primary productivity, the quantification of which could be useful in determining the magnitude and sign of the biogeochemical feedback on radiative forcing. However, the impact of elemental deposition to remote ocean regions is not well understood and is not currently included in global climate models. In this study, emission inventories for eight elements primarily of soil origin, Mg, P, Ca, Mn, Fe, K, Al, and Si are determined based on a global mineral data set and a soil data set. The resulting elemental fractions are used to drive the desert dust model in the Community Earth System Model (CESM) in order to simulate the elemental concentrations of atmospheric dust. Spatial variability of mineral dust elemental fractions is evident on a global scale, particularly for Ca. Simulations of global variations in the Ca / Al ratio, which typically range from around 0.1 to 5.0 in soils, are consistent with observations, suggesting that this ratio is a good signature for dust source regions. The simulated variable fractions of chemical elements are sufficiently different; estimates of deposition should include elemental variations, especially for Ca, Al and Fe. The model results have been evaluated with observations of elemental aerosol concentrations from desert regions and dust events in non-dust regions, providing insights into uncertainties in the modeling approach. The ratios between modeled and observed elemental fractions range from 0.7 to 1.6, except for Mg and Mn (3.4 and 3.5, respectively). Using the soil database improves the correspondence of the spatial heterogeneity in the modeling of several elements (Ca, Al and Fe) compared to observations. Total and soluble dust element fluxes to different ocean basins and ice sheet regions have been estimated, based on the model results. The annual inputs of soluble Mg, P, Ca, Mn, Fe and K associated with dust using the mineral data set are 0.30 Tg, 16.89 Gg, 1.32 Tg, 22.84 Gg, 0.068 Tg, and 0.15 Tg to global oceans and ice sheets.

Description: A major link between climate and humans in Northern Africa, and the Sahel in particular, is land use and associated land cover change, mainly where subsistence farming prevails. Here we assess possible feedbacks between the type of land use and harvest intensity and climate by analyzing a series of idealized GCM experiments using the MPI-ESM. The base line for these experiments is a simulation forced by the RCP8.5 scenario which includes strong greenhouse gas emissions and anthropogenic land cover changes. The anthropogenic land cover changes in the RCP8.5 scenario include a mixture of pasture and agriculture. In subsequent simulations, we replace the entire area affected by anthropogenic land cover change in the region between the Sahara in the North and the Guinean Coast in the South (4 to 20° N) by either pasture or agriculture, respectively. In a second setup we vary the amount of harvest in case of agriculture. The RCP8.5 base line simulation reveals strong changes in mean agriculture and monsoon rainfall. In comparison with these changes, any variation of the type of land use in the study area leads to very small, mostly insignificantly small, additional differences in mean temperature and annual precipitation change in this region. Within the uncertainty of the representation of land use in current ESMs, our study suggests marginal feedback between land use changes and climate changes triggered by strong greenhouse gas emissions. Hence as a good approximation, climate change can be considered as external driver in models of land-use – conflict dynamics when seasonal or mean values are used as external driver.

Description: The eastern part of the oceanic Cocos Plate presents a heterogeneous crustal structure due to diverse origins and ages as well as plate-hot spot interactions which originated the Cocos Ridge, a structure that converges with the Caribbean Plate in southeastern Costa Rica. The complex structure of the oceanic plate directly influences the dynamics and geometry of the subduction zone along the Middle American Trench. In this paper an integrated interpretation of the slab geometry in Costa Rica is presented based on 3-D density modeling of combined satellite and surface gravity data, constrained by available geophysical and geological data and seismological information obtained from local networks. The results show the continuation of steep subduction geometry from the Nicaraguan margin into northwestern Costa Rica, followed by a moderate dipping slab under the Central Cordillera toward the end of the Central American Volcanic Arc. Contrary to commonly assumed, to the southeast end of the volcanic arc, our preferred model shows a steep, coherent slab that extends up to the landward projection of the Panama Fracture Zone. Overall, a gradual change in the depth of the intraplate seismicity is observed, reaching 220 km in the northwestern part, and becoming progressively shallower toward the southeast, where it reaches a maximum depth of 75 km. The changes in the terminal depth of the observed seismicity correlate with the increased density in the modeled slab. The absence of intermediate depth (〉 75 km) intraplate seismicity in the southeastern section and the higher densities for the subducted slab in this area, support a model in which dehydration reactions in the subducted slab cease at a shallower depth, originating an anhydrous and thus aseismic slab.

Description: The Lena River forms one of the largest deltas in the Arctic. We compare two sets of data to reveal new insights into the hydrological, hydrochemical, and geochemical processes within the delta: (i) long-term hydrometric observations at the Khabarova station at the head of the delta from 1951 to 2005; (ii) field hydrological and geochemical observations carried out within the delta since 2002. Periods with differing relative discharge and intensity of fluvial processes were identified from the long-term record of water and sediment discharge. Ice events during spring melt (high water) reconfigured branch channels and probably influenced sediment transport within the delta. Based on summer field measurements during 2005–2012 of discharge and sediment fluxes along main delta channels, both are increased between the apex and the front of the delta. This increase is to a great extent connected with an additional influx of water from tributaries, as well as an increase of suspended and dissolved material released from the ice complex. Summer concentrations of major ion and biogenic substances along the delta branches are partly explained by water sources within the delta, such as thawing ice complex waters, small Lena River branches and estuarine areas.

Description: Concerning their sensitivity to ocean acidification, coccolithophores, a group of calcifying single-celled phytoplankton, are one of the best-studied groups of marine organisms. However, in spite of the large number of studies investigating coccolithophore physiological responses to ocean acidification, uncertainties still remain due to variable and partly contradictory results. In the present study we have used all existing data in a meta-analysis to estimate the effect size of future pCO2 changes on the rates of calcification and photosynthesis and the ratio of particulate inorganic to organic carbon (PIC / POC) in different coccolithophore species. Our results indicate that ocean acidification has a negative effect on calcification and the cellular PIC / POC ratio in the two most abundant coccolithophore species: Emiliania huxleyi and Gephyrocapsa oceanica. In contrast, the more heavily calcified species Coccolithus braarudii did not show a distinct response when exposed to elevated pCO2/reduced pH. Photosynthesis in Gephyrocapsa oceanica was positively affected by high CO2, while no effect was observed for the other coccolithophore species. There was no indication that the method of carbonate chemistry manipulation was responsible for the inconsistent results regarding observed responses in calcification and the PIC / POC ratio. The perturbation method, however, appears to affect photosynthesis, as responses varied significantly between total alkalinity (TA) and dissolved inorganic carbon (DIC) manipulations. These results emphasize that coccolithophore species respond differently to ocean acidification, both in terms of calcification and photosynthesis. Where negative effects occur, they become evident at CO2 levels in the range projected for this century in the case of unabated CO2 emissions. As the data sets used in this meta-analysis do not account for adaptive responses, ecological fitness and ecosystem interactions, the question remains as to how these physiological responses play out in the natural environment.

Description: The upper 500 m of the water column and the sediment surface along an E–W transect in the Fram Strait were sampled for recent planktic foraminifera. The δ18O and δ13C values of the tests are compared to the stable isotope composition of water samples taken from the same depths, and related to the characteristics of the water column. The polar species Neogloboquadrina pachyderma (sin.) clearly dominates the species assemblage in the Fram Strait in the early summer, while the subpolar Turborotalita quinqueloba accounts only for 5–23%. In this area the average depth of calcification of N. pachyderma (sin.) lies between 70–150m water depth, T. quinqueloba shows a similar range with 50–120 m water depth. The δ18O values of N. pachyderma (sin.) show an average vital effect of about −1.5‰ compared to calculated equilibrium calcite values. Except for the upper ~ 75 m, the vertical profiles of δ13C of the net-sampled shells are nearly parallel to the values measured in the water column with an average offset of −1.6‰ and −3.6‰ for N. pachyderma (sin.) and T. quinqueloba, respectively. The discrepancy found in the upper ~ 75 m might indicate the influence of the "carbonate ion effect" on the carbon isotope incorporation in the tests. Oxygen and carbon isotopes from the sediment surface yield higher values than those from the water column for both species. This may be because specimens from the water column reflect a modern snapshot only, while tests from surface sediments record environmental parameters from the past ~ 1000 years.

Description: Ocean observations carried out in the framework of the Collaborative Research Center 754 (SFB 754) "Climate-Biogeochemistry Interactions in the Tropical Ocean" are used to study (1) the structure of tropical oxygen minimum zones (OMZs), (2) the processes that contribute to the oxygen budget, and (3) long-term changes in the oxygen distribution. The OMZ of the eastern tropical North Atlantic (ETNA), located between the well-ventilated subtropical gyre and the equatorial oxygen maximum, is composed of a deep OMZ at about 400 m depth with its core region centred at about 20° W, 10° N and a shallow OMZ at about 100 m depth with lowest oxygen concentrations in proximity to the coastal upwelling region off Mauritania and Senegal. The oxygen budget of the deep OMZ is given by oxygen consumption mainly balanced by the oxygen supply due to meridional eddy fluxes (about 60%) and vertical mixing (about 20%, locally up to 30%). Advection by zonal jets is crucial for the establishment of the equatorial oxygen maximum. In the latitude range of the deep OMZ, it dominates the oxygen supply in the upper 300 to 400 m and generates the intermediate oxygen maximum between deep and shallow OMZs. Water mass ages from transient tracers indicate substantially older water masses in the core of the deep OMZ (about 120–180 years) compared to regions north and south of it. The deoxygenation of the ETNA OMZ during recent decades suggests a substantial imbalance in the oxygen budget: about 10% of the oxygen consumption during that period was not balanced by ventilation. Long-term oxygen observations show variability on interannual, decadal and multidecadal time scales that can partly be attributed to circulation changes. In comparison to the ETNA OMZ the eastern tropical South Pacific OMZ shows a similar structure including an equatorial oxygen maximum driven by zonal advection, but overall much lower oxygen concentrations approaching zero in extended regions. As the shape of the OMZs is set by ocean circulation, the widespread misrepresentation of the intermediate circulation in ocean circulation models substantially contributes to their oxygen bias, which might have significant impacts on predictions of future oxygen levels.

Description: Carbon cycling in Peruvian margin sediments (11° S and 12° S) was examined at 16 stations from 74 m on the inner shelf down to 1024 m water depth by means of in situ flux measurements, sedimentary geochemistry and modeling. Bottom water oxygen was below detection limit down to ca. 400 m and increased to 53 μM at the deepest station. Sediment accumulation rates and benthic dissolved inorganic carbon fluxes decreased rapidly with water depth. Particulate organic carbon (POC) content was lowest on the inner shelf and at the deep oxygenated stations (〈 5%) and highest between 200 and 400 m in the oxygen minimum zone (OMZ, 15–20%). The organic carbon burial efficiency (CBE) was unexpectedly low on the inner shelf (〈 20%) when compared to a global database, for reasons which may be linked to the frequent ventilation of the shelf by oceanographic anomalies. CBE at the deeper oxygenated sites was much higher than expected (max. 81%). Elsewhere, CBEs were mostly above the range expected for sediments underlying normal oxic bottom waters, with an average of 51 and 58% for the 11° S and 12° S transects, respectively. Organic carbon rain rates calculated from the benthic fluxes alluded to a very efficient mineralization of organic matter in the water column, with a Martin curve exponent typical of normal oxic waters (0.88 ± 0.09). Yet, mean POC burial rates were 2–5 times higher than the global average for continental margins. The observations at the Peruvian margin suggest that a lack of oxygen does not affect the degradation of organic matter in the water column but promotes the preservation of organic matter in marine sediments.

Description: The natural abundance of 14C in total CO2 dissolved in seawater is a property applied to evaluate the water age structure and circulation in the ocean and in ocean models. In this study we use three different representations of the global ocean circulation augmented with a suite of idealised tracers to study the potential and limitations of using natural 14C to determine water age, the time elapsed since a body of water had contact with the atmosphere. We find that, globally, bulk 14C-age is dominated by two equally important components, one associated with aging, i.e. the time component of circulation and one associated with a "preformed 14C-age". This latter quantity exists because of the slow and incomplete atmosphere/ocean equilibration of 14C in particular in high latitudes where many water masses form. The relative contribution of the preformed component to bulk 14C-age varies regionally within a given model, but also between models. Regional variability, e.g. in the Atlantic Ocean is associated with the mixing of waters with very different end members of preformed 14C-age. In the Atlantic, variations in the preformed component over space and time mask the circulation component to an extent that its patterns are not detectable from bulk 14C-age alone. Between models the variability of age can also be considerable (factor of 2), related to the combinations of physical model parameters, which influence circulation dynamics, and gas exchange in the models. The preformed component was found to be very sensitive to gas exchange and moderately sensitive to ice cover. In our model evaluation exercise, the choice of the gas exchange constant from within the current range of uncertainty had such a strong influence on preformed and bulk 14C-age that if model evaluation would be based on bulk 14C-age it could easily impair the evaluation and tuning of a models circulation on global and regional scales. Based on the results of this study, we propose that considering preformed 14C-age is critical for a correct assessment of circulation in ocean models.

Description: Extracellular release (ER) by phytoplankton is the major source of fresh dissolved organic carbon (DOC) in marine ecosystems and accompanies primary production during all growth phases. Little is known, so far, on size and composition of released molecules, and to which extent ER occurs passively, by leakage, or actively, by exudation. Here, we report on ER by the widespread and bloom-forming coccolithophore Emiliania huxleyi grown under steady state conditions in phosphorus controlled chemostats (N : P = 29, growth rate of μ = 0.2 d−1). 14C incubations were accomplished to determine primary production (PP), comprised by particulate (PO14C) and dissolved organic carbon (DO14C), and the concentration and composition of particulate combined carbohydrates (pCCHO), and of high molecular weight (〉1 kDa, HMW) dissolved combined carbohydrates (dCCHO) as major components of ER. Information on size distribution of ER products was obtained by investigating distinct size classes (〈0.40 μm, 〈1000 kDa, 〈100 kDa and 〈10 kDa) of DO14C and HMW-dCCHO. Our results revealed relatively low ER during steady state growth, corresponding to ∼4.5% of primary production, and similar ER rates for all size classes. Acidic sugars had a significant share on freshly produced pCCHO as well as on HMW-dCCHO. While pCCHO and the smallest size (〈10 kDa) fraction of HMW-dCCHO exhibited a similar sugar composition, dominated by high percentages of glucose (74–80 Mol%), the composition of HMW-dCCHO size-classes 〉10 kDa was significantly different with higher Mol% of arabinose. Mol% of acidic sugars increased and Mol% glucose decreased with increasing size of HMW-dCCHO. We conclude that larger polysaccharides follow different production and release pathways than smaller molecules, potentially serving distinct ecological and biogeochemical functions.

Description: For this study two sediment cores from the Peruvian shelf covering the time period between the Little Ice Age (LIA) and present were examined for changes in productivity (biogenic opal concentrations (bSi)), nutrient utilisation (stable isotope compositions of silicon (δ30Siopal) and nitrogen (δ15Nsed)), as well as in ocean circulation and material transport (authigenic and detrital radiogenic neodymium (εNd) and strontium (87Sr/86Sr) isotopes). For the LIA the proxies recorded weak primary productivity and nutrient utilisation reflected by low average bSi concentrations of ~10%, δ15Nsed values of ~ +5‰ and intermediate δ30Siopal values of ~+0.97‰. At the same time the radiogenic isotope composition of the detrital sediment fraction indicates dominant local riverine input of lithogenic material due to higher rainfall in the Andean hinterland. These patterns were caused by permanent El Niño-like conditions characterized by a deeper nutricline, weak upwelling and low nutrient supply. At the end of the LIA, δ30Siopal dropped to low values of +0.6‰ and opal productivity reached its minimum of the past 650 years. During the following transitional period of time the intensity of upwelling, nutrient supply and productivity increased abruptly as marked by the highest bSi contents of up to 38%, by δ15Nsed of up to ~ +7‰, and by the highest degree of silicate utilisation with δ30Siopal reaching values of +1.1‰. At the same time detrital εNd and 87Sr/86Sr signatures documented increased wind strength and supply of dust to the shelf due to drier conditions. Since about 1870, productivity has been high but nutrient utilisation has remained at levels similar to the LIA indicating significantly increased nutrient availability. Comparison between the δ30Siopal and δ15Nsed signatures suggests that during the past 650 years the δ15Nsed signature in the Peruvian Upwelling area has most likely primarily been controlled by surface water utilisation and not, as previously assumed, by subsurface nitrogen loss processes in the water column.

Description: Currently available transient tracers have different application ranges that are defined by their temporal input (chronological transient tracers) or their decay rate (radioactive transient tracers). Transient tracers range from tracers for highly ventilated water masses such as sulfur hexafluoride (SF6) through tritium (3H) and chlorofluorocarbons (CFCs) up to tracers for less ventilated deep ocean basins such as argon-39 (39Ar) and radiocarbon (14C). In this context, highly ventilated water masses are defined as water masses that have been in contact with the atmosphere during the last decade. Transient tracers can be used to empirically constrain the transit time distribution (TTD), which can often be approximated with an inverse Gaussian (IG) distribution. The IG-TTD provides information about ventilation and the advective/diffusive characteristics of a water parcel. Here we provide an overview of commonly used transient tracer couples and the corresponding application range of the IG-TTD by using the new concept of validity areas. CFC-12, CFC-11 and SF6 data from three different cruises in the South Atlantic Ocean and Southern Ocean as well as 39Ar data from the 1980s and early 1990s in the eastern Atlantic Ocean and the Weddell Sea are used to demonstrate this method. We found that the IG-TTD can be constrained along the Greenwich Meridian south to 46° S, which corresponds to the Subantarctic Front (SAF) denoting the application limit. The Antarctic Intermediate Water (AAIW) describes the limiting water layer in the vertical. Conspicuous high or lower ratios between the advective and diffusive components describe the transition between the validity area and the application limit of the IG-TTD model rather than describing the physical properties of the water parcel. The combination of 39Ar and CFC data places constraints on the IG-TTD in the deep water north of the SAF, but not beyond this limit.

Description: Local coupling between nitrogen fixation and denitrification in current biogeochemical models could result in runaway feedback in open-ocean oxygen minimum zones (OMZs), eventually stripping OMZ waters of all fixed nitrogen. This feedback does not seem to operate at full strength in the ocean, as nitrate does not generally become depleted in open-ocean OMZs. To explore in detail the possible mechanisms that prevent nitrogen depletion in the OMZ of the eastern tropical South Pacific (ETSP), we develop a box model with fully prognostic cycles of carbon, nutrients and oxygen in the upwelling region and its adjacent open ocean. Ocean circulation is calibrated with Δ14C data of the ETSP. The sensitivity of the simulated nitrogen cycle to nutrient and oxygen exchange and ventilation from outside the model domain and to remineralization scales inside an OMZ is analysed. For the entire range of model configurations explored, we find that the fixed-N inventory can be stabilized at non-zero levels in the ETSP OMZ only if the remineralization rate via denitrification is slower than that via aerobic respiration. In our optimum model configuration, lateral oxygen supply into the model domain is required at rates sufficient to oxidize at least about one fifth of the export production in the model domain to prevent anoxia in the deep ocean. Under these conditions, our model is in line with the view of phosphate as the ultimate limiting nutrient for phytoplankton, and implies that for the current notion of nitrogen fixation being favoured in N-deficit waters, the water column of the ETSP could even be a small net source of nitrate.

Description: The recently observed variability in the tropical tropopause layer (TTL), which features a warming of 0.9 K over the past decade (2001–2011), is investigated with a number of sensitivity experiments from simulations with NCAR's CESM-WACCM chemistry–climate model. The experiments have been designed to specifically quantify the contributions from natural as well as anthropogenic factors, such as solar variability (Solar), sea surface temperatures (SSTs), the quasi-biennial oscillation (QBO), stratospheric aerosols (Aerosol), greenhouse gases (GHGs) and the dependence on the vertical resolution in the model. The results show that, in the TTL from 2001 through 2011, a cooling in tropical SSTs leads to a weakening of tropical upwelling around the tropical tropopause and hence relative downwelling and adiabatic warming of 0.3 K decade-1; stronger QBO westerlies result in a 0.2 K decade-1 warming; increasing aerosols in the lower stratosphere lead to a 0.2 K decade-1 warming; a prolonged solar minimum contributes about 0.2 K decade-1 to a cooling; and increased GHGs have no significant influence. Considering all the factors mentioned above, we compute a net 0.5 K decade-1 warming, which is less than the observed 0.9 K decade-1 warming over the past decade in the TTL. Two simulations with different vertical resolution show that, with higher vertical resolution, an extra 0.8 K decade-1 warming can be simulated through the last decade compared with results from the "standard" low vertical resolution simulation. Model results indicate that the recent warming in the TTL is partly caused by stratospheric aerosols and mainly due to internal variability, i.e. the QBO and tropical SSTs. The vertical resolution can also strongly influence the TTL temperature response in addition to variability in the QBO and SSTs.

Description: Large amounts of methane are delivered by fluids through the erosive forearc of the convergent margin offshore Costa Rica and lead to the formation of cold seeps at the sediment surface. Besides mud extrusion, numerous cold seeps are created by landslides induced by seamount subduction or fluid migration along major faults. Most of the dissolved methane reaching the seafloor at cold seeps is oxidized within the benthic microbial methane filter by anaerobic oxidation of methane (AOM). Measurements of AOM and sulfate reduction as well as numerical modeling of porewater profiles revealed a highly active and efficient benthic methane filter at Quepos Slide site; a landslide on the continental slope between the Nicoya and Osa Peninsula. Integrated areal rates of AOM ranged from 12.9 ± 6.0 to 45.2 ± 11.5 mmol m-2 d-1, with only 1 to 2.5% of the upward methane flux being released into the water column. Additionally, two parallel sediment cores from Quepos Slide were used for in vitro experiments in a recently developed Sediment-F low-Through (SLOT) system to simulate an increased fluid and methane flux from the bottom of the sediment core. The benthic methane filter revealed a high adaptability whereby the methane oxidation efficiency responded to the increased fluid flow within 150–170 days. To our knowledge, this study provides the first estimation of the natural biogeochemical response of seep sediments to changes in fluid flow.

Description: A large, subsurface oxygen deficiency zone is located in the eastern tropical South Pacific Ocean (ETSP). The large-scale circulation in the eastern equatorial Pacific and off Peru in November/December 2012 shows the influence of the equatorial current system, the eastern boundary currents, and the northern reaches of the subtropical gyre. In November 2012 the Equatorial Undercurrent is centered at 250 m depth, deeper than in earlier observations. In December 2012 the equatorial water is transported southeastward near the shelf in the Peru-Chile Undercurrent with a mean transport of 1.6 Sv. In the oxygen minimum zone (OMZ) the flow is overlaid with strong eddy activity on the poleward side of the OMZ. Floats with parking depth at 400 m show fast westward flow in the mid-depth equatorial channel and sluggish flow in the OMZ. Floats with oxygen sensors clearly show the passage of eddies with oxygen anomalies. The long-term float observations in the upper ocean lead to a net community production estimate at about 18° S of up to 16.7 mmol C m−3 yr1 extrapolated to an annual rate and 7.7 mmol C m−3 yr−1 for the time period below the mixed layer. Oxygen differences between repeated ship sections are influenced by the Interdecadal Pacific Oscillation, by the phase of El Niño, by seasonal changes, and by eddies and hence have to be interpreted with care. At and south of the equator the decrease in oxygen in the upper ocean since 1976 is related to an increase in nitrate, phosphate, and in part in silicate.

Description: Slant-integrated water vapor (SIWV) data derived from GPS STDs (slant total delays), which provide the spatial information on tropospheric water vapor, have a high potential for assimilation to weather models or for nowcasting or reconstruction of the 3-D humidity field with tomographic techniques. Therefore, the accuracy of GPS STD is important, and independent observations are needed to estimate the quality of GPS STD. In 2012 the GFZ (German Research Centre for Geosciences) started to operate a microwave radiometer in the vicinity of the Potsdam GPS station. The water vapor content along the line of sight between a ground station and a GPS satellite can be derived from GPS data and directly measured by a water vapor radiometer (WVR) at the same time. In this study we present the validation results of SIWV observed by a ground-based GPS receiver and a WVR. The validation covers 184 days of data with dry and wet humidity conditions. SIWV data from GPS and WVR generally show good agreement with a mean bias of −0.4 kg m−2 and an rms (root mean square) of 3.15 kg m−2. The differences in SIWV show an elevation dependent on an rms of 7.13 kg m−2 below 15° but of 1.76 kg m−2 above 15°. Nevertheless, this elevation dependence is not observed regarding relative deviations. The relation between the differences and possible influencing factors (elevation angles, pressure, temperature and relative humidity) are analyzed in this study. Besides the elevation, dependencies between the atmospheric humidity conditions, temperature and the differences in SIWV are found.

Description: Marine biological production as well as the associated biotic uptake of carbon in many ocean regions depends on the availability of nutrients in the euphotic zone. While large areas are limited by nitrogen and/or phosphorus, the micronutrient iron is considered the main limiting nutrient in the North Pacific, equatorial Pacific and Southern Ocean. Changes in iron availability via changes in atmospheric dust input are discussed to play an important role in glacial–interglacial cycles via climate feedbacks caused by changes in biological ocean carbon sequestration. Although many aspects of the iron cycle remain unknown, its incorporation into marine biogeochemical models is needed to test our current understanding and better constrain its role in the Earth system. In the University of Victoria Earth System Climate Model (UVic) iron limitation in the ocean was, until now, simulated pragmatically with an iron concentration masking scheme that did not allow a consistent interactive response to perturbations of ocean biogeochemistry or iron cycling sensitivity studies. Here, we replace the iron masking scheme with a dynamic iron cycle and compare the results to available observations and the previous marine biogeochemical model. Sensitivity studies are also conducted with the new model to test the sensitivity of the model to parameterized iron ligand concentrations, the importance of considering the variable solubility of iron in dust deposition, the importance of considering high-resolution bathymetry for the sediment release of iron, the effect of scaling the sedimentary iron release with temperature and the sensitivity of the iron cycle to a climate change scenario.

Description: A comparative study of simultaneous heat and gas exchange measurements was performed in the large annular Heidelberg Air–Sea Interaction Facility, the Aeolotron, under homogeneous water surface conditions. The use of two gas tracers, N2O and C2HF5, resulted not only in gas transfer velocities, but also in the measurement of the Schmidt number exponent n with a precision of ± 0.025. The original controlled flux or active thermographic technique proposed by Jähne et al. (1989) was applied by heating a large patch at the water surface to measure heat transfer velocities. Heating a large patch, the active thermography technique is laterally homogeneous and problems of lateral transport effects are avoided. Using the measured Schmidt number exponents, the ratio of the scaled heat transfer velocities to the measured gas transfer velocities is 1.046 ± 0.040, a good agreement within the limits of experimental uncertainties. This indicates the possibility to scale heat transfer velocities measured by active thermography to gas transfer velocities, provided the Schmidt number exponent is known and that the heated patch is large enough to reach the thermal equilibrium.

Description: Here we present first observations, from instrumentation installed on moorings and a float, of unexpectedly low (〈2 μmol kg−1) oxygen environments in the open waters of the tropical North Atlantic, a region where oxygen concentration does normally not fall much below 40 μmol kg−1. The low-oxygen zones are created at shallow depth, just below the mixed layer, in the euphotic zone of cyclonic eddies and anticyclonic-modewater eddies. Both types of eddies are prone to high surface productivity. Net respiration rates for the eddies are found to be 3 to 5 times higher when compared with surrounding waters. Oxygen is lowest in the centre of the eddies, in a depth range where the swirl velocity, defining the transition between eddy and surroundings, has its maximum. It is assumed that the strong velocity at the outer rim of the eddies hampers the transport of properties across the eddies boundary and as such isolates their cores. This is supported by a remarkably stable hydrographic structure of the eddies core over periods of several months. The eddies propagate westward, at about 4 to 5 km day−1, from their generation region off the West African coast into the open ocean. High productivity and accompanying respiration, paired with sluggish exchange across the eddy boundary, create the "dead zone" inside the eddies, so far only reported for coastal areas or lakes. We observe a direct impact of the open ocean dead zones on the marine ecosystem as such that the diurnal vertical migration of zooplankton is suppressed inside the eddies.

Description: The Mediterranean Sea is considered a "hot spot" for climate change, being characterized by oligotrophic to ultra-oligotrophic waters and rapidly increasing seasurface temperature and changing carbonate chemistry. Coccolithophores are considered a dominant phytoplankton group in these waters. As marine calcifying organisms they are expected to respond to the ongoing changes in seawater carbonate chemistry. We provide here a description of the springtime coccolithophore distribution in the Mediterranean Sea and relate this to a broad set of in situ-measured environmental variables. Samples were taken during the R/V Meteor (M84/3) oceanographic cruise in April 2011, between 0 and 100 m water depth from 28 stations. Total diatom and silicoflagellate cell concentrations are also presented. Our results highlight the importance of seawater carbonate chemistry, especially [CO32−] but also [PO43−] in unraveling the distribution of heterococcolithophores, the most abundant coccolithophore life phase. Holo- and heterococcolithophores respond differently to environmental factors. For instance, changes in heterococcolithophore assemblages were best linked to the combination of [CO32−], pH, and salinity (ρ = 0.57), although salinity might be not functionally related to coccolithophore assemblage distribution. Holococcolithophores, on the other hand, showed higher abundances and species diversity in oligotrophic areas (best fit, ρ = 0.32 for nutrients), thriving in nutrient-depleted waters. Clustering of heterococcolithophores revealed three groups of species sharing more than 65% similarities. These clusters could be assigned to the eastern and western basins and deeper layers (below 50 m), respectively. In addition, the species Gephyrocapsa oceanica, G. muellerae, and Emiliania huxleyi morphotype B/C are spatially distributed together and trace the influx of Atlantic waters into the Mediterranean Sea. The results of the present work emphasize the importance of considering holo- and heterococcolithophores separately when analyzing changes in species assemblages and diversity. Our findings suggest that coccolithophores are a main phytoplankton group in the entire Mediterranean Sea and can dominate over siliceous phytoplankton. They have life stages that are expected to respond differently to the variability in seawater carbonate chemistry and nutrient concentrations.