ALBERT

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: Variability and trends in seasonal and interannual ice area export out of the Laptev Sea between 1992 and 2011 are investigated using satellite-based sea ice drift and concentration data. We found an average total winter (October to May) ice area transport across the northern and eastern Laptev Sea boundaries (NB and EB) of 3.48 × 10hoch5 km2. The average transport across the NB (2.87 × 10hoch5 km2)is thereby higher than across the EB (0.61 × 10hoch5 km2), with a less pronounced seasonal cycle. The total Laptev Sea ice area flux significantly increased over the last decades (0.85 × 10hoch5 km2 decade−1, p 〉 0.95), dominated by increasing export through the EB (0.55 × 10hoch5 km2 decade−1, p 〉 0.90), while the increase in export across the NB is smaller (0.3 × 10hoch5 km2 decade−1) and statistically not significant. The strong coupling between across-boundary SLP gradient and ice drift velocity indicates that monthly variations in ice area flux are primarily controlled by changes in geostrophic wind velocities, although the Laptev Sea ice circulation shows no clear relationship with large-scale atmospheric indices. Also there is no evidence of increasing wind velocities that could explain the overall positive trends in ice export. The increased transport rates are rather the consequence of a changing ice cover such as thinning and/or a decrease in concentration. The use of a back-propagation method revealed that most of the ice that is incorporated into the Transpolar Drift is formed during freeze-up and originates from the central and western part of the Laptev Sea, while the exchange with the East Siberian Sea is dominated by ice coming from the central and southeastern Laptev Sea. Furthermore, our results imply that years of high ice export in late winter (February to May) have a thinning effect on the ice cover, which in turn preconditions the occurence of negative sea ice extent anomalies in summer.

Description: To examine the potentially competing influences of microzooplankton and calcite mineral ballast on organic matter remineralization, we incubated diatoms in darkness in rolling tanks with and without added calcite minerals (coccoliths) and microzooplankton (rotifers). Concentrations of particulate organic matter (POM in suspension or in aggregates), of dissolved organic matter (DOM), and of dissolved inorganic nutrients were monitored over 8 days. The presence of rotifers enhanced the remineralization of ammonium and phosphate, but not dissolved silicon, from the biogenic particulate matter, up to 40% of which became incorporated into aggregates early in the experiment. Added calcite resulted in rates of excretion of ammonium and phosphate by rotifers that were depressed by 67% and 36%, respectively, demonstrating the potential for minerals to inhibit the destruction of POM by zooplankton in the water column. Lastly, the presence of the rotifers and added calcite minerals resulted in a more rapid initial rate of aggregation, although not a greater overall amount of aggregation during the experiment.

Description: Meridional and vertical distributions of several biogeochemical parameters were studied along a section in the southeastern Atlantic and the Southern Ocean south of South Africa during the austral summer 2008 of the International Polar Year to characterize the biogeochemical provinces and to assess the seasonal net diatom production. Based on analyses of macro-nutrients, ammonium (NH4), chlorophyll a, (Chl a), phaeopigments, biogenic silica (BSi), particulate inorganic carbon (PIC), and particulate organic carbon and nitrogen (POC and PON, respectively), four biogeochemical domains were distinguished along the section: the subtropical Atlantic, the confluence zone of the subtropical and subantarctic domains, the Polar Frontal Zone (PFZ) in the Antarctic Circumpolar Current (ACC), and the north-eastern branch of the Weddell Gyre. The subtropical region displayed extremely low nutrient concentrations featuring oligotrophic conditions, and sub-surface maxima of Chl a and phaeopigments never exceeded 0.5 µg L−1 and 0.25 µg L−1, respectively. The anticyclonic and cyclonic eddies crossed in the Cape Basin were characterized by a deepening and a rise, respectively, of the nutrients isoclines. The confluence zone of the subtropical domain and the northern side of the ACC within the subantarctic domain displayed remnant nitrate and phosphate levels, whereas silicate concentrations kept to extremely low levels. In this area, Chl a level of 0.4–0.5 µg L−1 distributed homogenously within the mixed layer, and POC and PON accumulated to values up to 10 µM and 1.5 µM, respectively, indicative of biomass accumulation along the confluence zone during the late productive period. In the ACC domain, the Polar Frontal Zone was marked by a post-bloom of diatoms that extended beyond the Polar Front (PF) during this late summer condition, as primarily evidenced by the massive depletion of silicic acid in the surface waters. The accumulation of NH4 to values up to 1.25 µM at 100 m depth centred on the PF and the accumulation of BSi up to 0.5 µM in the surface waters of the central part of the PFZ also featured a late stage of the seasonal diatom bloom. The silica daily net production rate based on the seasonal depletion of silicic acid was estimated to be 11.9 ± 6.5 mmol m−2 d−1 in the domain of the vast diatom post-bloom, agreeing well with the previously recorded values in this province. The Weddell Gyre occasionally displayed relative surface depletion of silicic acid, suggesting a late stage of a relatively minor diatom bloom possibly driven by iceberg drifting releases of iron. In this domain the estimated range of silica daily net production rate (e.g. 21.1 ± 8.8 mmol m−2 d−1) is consistent with previous studies, but was not significantly higher than that in the Polar Front region.

Description: As part of the Bonus-GoodHope (BGH) campaign, 15N-labelled nitrate, ammonium and urea uptake measurements were made along the BGH transect from Cape Town to ~60° S in late austral summer, 2008. Our results are categorised according to distinct hydrographic regions defined by oceanic fronts and open ocean zones. High regenerated nitrate uptake rate in the oligotrophic Subtropical Zone (STZ) resulted in low f-ratios (f = 0.2) with nitrogen uptake being dominated by ρurea, which contributed up to 70 % of total nitrogen uptake. Size fractionated chlorophyll data showed that the greatest contribution (〉50 %) of picophytoplankton (〈2 μm) were found in the STZ, consistent with a community based on regenerated production. The Subantarctic Zone (SAZ) showed the greatest total integrated nitrogen uptake (10.3 mmol m−2 d−1), mainly due to enhanced nutrient supply within an anticyclonic eddy observed in this region. A decrease in the contribution of smaller size classes to the phytoplankton community was observed with increasing latitude, concurrent with a decrease in the contribution of regenerated production. Higher f-ratios observed in the SAZ (f = 0.49), Polar Frontal Zone (f= 0.41) and Antarctic Zone (f = 0.45) relative to the STZ (f = 0.24), indicate a higher contribution of NO3−-uptake relative to total nitrogen and potentially higher export production. High ambient regenerated nutrient concentrations are indicative of active regeneration processes throughout the transect and ascribed to late summer season sampling. Higher depth integrated uptake rates also correspond with higher surface iron concentrations. No clear correlation was observed between carbon export estimates derived from new production and 234Th flux. In addition, export derived from 15N estimates were 2–20 times greater than those based on 234Th flux. Variability in the magnitude of export is likely due to intrinsically different methods, compounded by differences in integration time scales for the two proxies of carbon export.

Description: Knowledge of calcium phosphate (Ca-P) solubility is crucial for understanding temporal and spatial variations of phosphorus (P) concentrations in water bodies and sedimentary reservoirs. In situ relationships between liquid-and solid-phase levels cannot be fully explained by dissolved analytes alone and need to be verified by determining particular sediment P species. Lack of quantification methods for these species limits the knowledge of the P cycle. To address this issue, we (i) optimized a specifically developed conversion-extraction (CONVEX) method for P species quantification using standard additions, and (ii) simultaneously determined solubilities of Ca-P standards by measuring their pH-dependent contents in the sediment matrix. Ca-P minerals including various carbonate fluorapatite (CFAP) specimens from different localities, fluorapatite (FAP), fish bone apatite, synthetic hydroxylapatite (HAP) and octacalcium phosphate (OCP) were characterized by XRD, Raman, FTIR and elemental analysis. Sediment samples were incubated with and without these reference minerals and then sequentially extracted to quantify Ca-P species by their differential dissolution at pH values between 3 and 8. The quantification of solid-phase phosphates at varying pH revealed solubilities in the following order: OCP〉 HAP〉 CFAP (4.5% CO3)〉 CFAP (3.4% CO3)〉 CFAP (2.2% CO3)〉 FAP. Thus, CFAP was less soluble in sediment than HAP, and CFAP solubility increased with carbonate content. Unspiked sediment analyses together with standard addition analyses indicated consistent differential dissolution of natural sediment species vs. added reference species and therefore verified the applicability of the CONVEX method in separately determining the most prevalent Ca-P minerals. We found surprisingly high OCP contents in the coastal sediments analyzed, which supports the hypothesis of apatite formation by an OCP precursor mechanism.

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

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

Description: Seawater concentrations of the four brominated trace gases dibromomethane (CH2Br2), bromodichloromethane (CHBrCl2), dibromochloromethane (CHBr2Cl) and bromoform (CHBr3) were measured at different depths of the water column in the Iberian upwelling off Portugal during summer 2007. Bromocarbon concentrations showed elevated values in recently upwelled and aged upwelled waters (mean values of 30 pmol L−1 for CHBr3), while values in the open ocean were significantly lower (7.4 pmol L−1 for CHBr3). Correlations with biological variables and marker pigments indicated that phytoplankton could be identified as a weak bromocarbon source in the open ocean. In upwelled water masses along the coast, halocarbons were not correlated to Chl-a, indicating an external source, overlapping the possible internal production by phytoplankton. We showed that the tidal frequency had a significant influence on halocarbon concentrations in the upwelling and we linked those findings to a strong intertidal coastal source, as well as to a transport of those halocarbon enriched coastal waters by westward surface upwelling currents. Coastal sources and transport can be accounted for maximum values of up to 185.1 pmol L−1 CHBr3 in the upwelling. Comparison with other productive marine areas revealed that the Iberian upwelling had stronger halocarbon sources than the phytoplankton dominated sources in the Mauritanian upwelling. However, the concentrations off the Iberian Peninsula were still much lower than those of coastal macroalgal influenced waters or those of polar regions dominated by cold water adapted diatoms

Description: In this paper, we present a detailed evaluation of cross wavelet analysis of bivariate time series. We develop a statistical test for zero wavelet coherency based on Monte Carlo simulations. If at least one of the two processes considered is Gaussian white noise, an approximative formula for the critical value can be utilized. In a second part, typical pitfalls of wavelet cross spectra and wavelet coherency are discussed. The wavelet cross spectrum appears to be not suitable for significance testing the interrelation between two processes. Instead, one should rather apply wavelet coherency. Furthermore we investigate problems due to multiple testing. Based on these results, we show that coherency between ENSO and NAO is an artefact for most of the time from 1900 to 1995. However, during a distinct period from around 1920 to 1940, significant coherency between the two phenomena occurs.

Description: We study the inference of long-range correlations by means of Detrended Fluctuation Analysis (DFA) and argue that power-law scaling of the fluctuation function and thus long-memory may not be assumed a priori but have to be established. This requires the investigation of the local slopes. We account for the variability characteristic for stochastic processes by calculating empirical confidence regions. Comparing a long-memory with a short-memory model shows that the inference of long-range correlations from a finite amount of data by means of DFA is not specific. We remark that scaling cannot be concluded from a straight line fit to the fluctuation function in a log-log representation. Furthermore, we show that a local slope larger than α=0.5 for large scales does not necessarily imply long-memory. We also demonstrate, that it is not valid to conclude from a finite scaling region of the fluctuation function to an equivalent scaling region of the autocorrelation function. Finally, we review DFA results for the Prague temperature data set and show that long-range correlations cannot not be concluded unambiguously.

Description: A steady state box model was developed to estimate the methane input into the Black Sea water column at various water depths. Our model results reveal a total input of methane of 4.7 Tg yr−1. The model predicts that the input of methane is largest at water depths between 600 and 700 m (7% of the total input), suggesting that the dissociation of methane gas hydrates at water depths equivalent to their upper stability limit may represent an important source of methane into the water column. In addition we discuss the effects of massive short-term methane inputs (e.g. through eruptions of deep-water mud volcanoes or submarine landslides at intermediate water depths) on the water column methane distribution and the resulting methane emission to the atmosphere. Our non-steady state simulations predict that these inputs will be effectively buffered by intense microbial methane consumption and that the upward flux of methane is strongly hampered by the pronounced density stratification of the Black Sea water column. For instance, an assumed input of methane of 179 Tg CH4 d−1 (equivalent to the amount of methane released by 1000 mud volcano eruptions) at a water depth of 700 m will only marginally influence the sea/air methane flux increasing it by only 3%.

Description: The interaction between iron availability and the phytoplankton elemental composition was investigated during the in situ iron fertilization experiment EIFEX and in laboratory experiments with the Southern Ocean diatom species Fragilariopsis kerguelensis and Chaetoceros dichaeta. Contrary to other in situ iron fertilization experiments we observed an increase in the BSi:POC, BSi:PON, and BSi:POP ratios within the iron fertilized patch during EIFEX. This is possibly caused by a relatively stronger increase in diatom abundance compared to other phytoplankton groups and does not necessarily represent the amount of silicification of single diatom cells. In laboratory experiments with F. kerguelensis and C. dichaeta no changes in the POC:PON, PON:POP, and POC:POP ratios were found with changing iron availability in both species. BSi:POC, BSi:PON, and BSi:POP ratios were significantly lower in the high iron treatments compared to the controls. In F. kerguelensis this was caused by a decrease in cellular BSi concentrations and therefore possibly less silicification. In C. dichaeta no change in cellular BSi concentration was found. Here lower BSi:POC, BSi:PON, and BSi:POP ratios were caused by an increase in cellular C, N, and P under high iron conditions. These results indicate that iron limitation does not always increase silicification in diatoms and that changes in the BSi:POC, BSi:PON, and BSi:POP ratios under iron fertilization in the field are caused by a variety of different mechanisms. Our results therefore imply that simple cause-and-effect relationships are not always applicable for modeling of elemental ratios.

Description: The subtropical Indian Ocean along 32° S was for the first time simultaneously sampled in 2002 for inorganic carbon and transient tracers. The vertical distribution and inventory of anthropogenic carbon (CANT) from five different methods: four data-base methods (ΔC*, TrOCA, TTD and IPSL) and a simulation from the OCCAM model are compared and discussed along with the observed CFC-12 and CCl4 distributions. In the surface layer, where carbon-based methods are uncertain, TTD and OCCAM yield the same result (7±0.2 molC m−2), helping to specify the surface CANT inventory. Below the mixed-layer, the comparison suggests that CANT penetrates deeper and more uniformly into the Antarctic Intermediate Water layer limit than estimated from the much utilized ΔC* method. Significant CFC-12 and CCl4 values are detected in bottom waters, associated with Antarctic Bottom Water. In this layer, except for ΔC* and OCCAM, the other methods detect significant CANT values. Consequently, the lowest inventory is calculated using the ΔC* method (24±2 molC m−2) or OCCAM (24.4±2.8 molC m−2) while TrOCA, TTD, and IPSL lead to higher inventories (28.1±2.2, 28.9±2.3 and 30.8±2.5 molC m−2 respectively). Overall and despite the uncertainties each method is evaluated using its relationship with tracers and the knowledge about water masses in the subtropical Indian Ocean. Along 32° S our best estimate for the mean CANT specific inventory is 28±2 molC m−2. Comparison exercises for data-based CANT methods along with time-series or repeat sections analysis should help to identify strengths and caveats in the CANT methods and to better constrain model simulations.

Description: A number of field-campaigns in the tropics have been conducted in recent years with two different LIDAR systems at Paramaribo (5.8° N, 55.2° W), Suriname. The lidars detect particles in the atmosphere with high vertical and temporal resolution and are capable of detecting extremely thin cloud layers which frequently occur in the tropical tropopause layer (TTL). Radiosonde as well as operational ECMWF analysis showed that equatorial Kelvin waves propagated in the TTL and greatly modulated its temperature structure. We found a clear correlation between the temperature anomalies introduced by these waves and the occurrence of thin cirrus in the TTL. In particular we found that extremely thin ice clouds form regularly where cold anomalies shift the tropopause to high altitudes. These findings suggest an influence of Kelvin wave activity on the dehydration in the TTL and thus on the global stratospheric water vapour concentration.

Description: The relation between the Agulhas Current retroflection location and the magnitude of Agulhas leakage, the transport of water from the Indian to the Atlantic Ocean, is investigated in a high-resolution numerical ocean model. Sudden eastward retreats of the Agulhas Current retroflection loop are linearly related to the shedding of Agulhas rings, where larger retreats generate larger rings. Using numerical Lagrangian floats a 37 year time series of the magnitude of Agulhas leakage in the model is constructed. The time series exhibits large amounts of variability, both on weekly and annual time scales. A linear relation is found between the magnitude of Agulhas leakage and the location of the Agulhas Current retroflection, both binned to three month averages. In the relation, a more westward location of the Agulhas Current retroflection corresponds to an increased transport from the Indian Ocean to the Atlantic Ocean. When this relation is used in a linear regression and applied to almost 20 years of altimetry data, it yields a best estimate of the mean magnitude of Agulhas leakage of 13.2 Sv. The early retroflection of 2000, when Agulhas leakage was probably halved, can be identified using the regression.

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

Description: The marine aragonite cycle has been included in the global biogeochemical model PISCES to study the role of aragonite in shallow water CaCO3 dissolution. Aragonite production is parameterized as a function of mesozooplankton biomass and aragonite saturation state of ambient waters. Observation-based estimates of marine carbonate production and dissolution are well reproduced by the model and about 60% of the combined CaCO3 water column dissolution from aragonite and calcite is simulated above 2000 m. In contrast, a calcite-only version yields a much smaller fraction. This suggests that the aragonite cycle should be included in models for a realistic representation of CaCO3 dissolution and alkalinity. For the SRES A2 CO2 scenario, production rates of aragonite are projected to notably decrease after 2050. By the end of this century, global aragonite production is reduced by 29% and total CaCO3 production by 19% relative to pre-industrial. Geographically, the effect from increasing atmospheric CO2, and the subsequent reduction in saturation state, is largest in the subpolar and polar areas where the modeled aragonite production is projected to decrease by 65% until 2100.

Description: Fully coupled climate carbon cycle models are sophisticated tools that are used to predict future climate change and its impact on the land and ocean carbon cycles. These models should be able to adequately represent natural variability, requiring model validation by observations. The present study focuses on the ocean carbon cycle component, in particular the spatial and temporal variability in net primary productivity (PP) and export production (EP) of particulate organic carbon (POC). Results from three coupled climate carbon cycle models (IPSL, MPIM, NCAR) are compared with observation-based estimates derived from satellite measurements of ocean colour and results from inverse modelling (data assimilation). Satellite observations of ocean colour have shown that temporal variability of PP on the global scale is largely dominated by the permanently stratified, low-latitude ocean (Behrenfeld et al., 2006) with stronger stratification (higher sea surface temperature; SST) being associated with negative PP anomalies. Results from all three coupled models confirm the role of the low-latitude, permanently stratified ocean for anomalies in globally integrated PP, but only one model (IPSL) also reproduces the inverse relationship between stratification (SST) and PP. An adequate representation of iron and macronutrient co-limitation of phytoplankton growth in the tropical ocean has shown to be the crucial mechanism determining the capability of the models to reproduce observed interactions between climate and PP.

Description: A set of experiments utilizing different implementations of the global ORCA-LIM model with horizontal resolutions of 2°, 0.5° and 0.25° is used to investigate tropical and extra-tropical influences on equatorial Pacific SST variability at interannual to decadal time scales. The model experiments use a bulk forcing methodology building on the global forcing data set for 1958 to 2000 developed by Large and Yeager (2004) that is based on a blend of atmospheric reanalysis data and satellite products. Whereas representation of the mean structure and transports of the (sub-) tropical Pacific current fields is much improved with the enhanced horizontal resolution, there is only little difference in the simulation of the interannual variability in the equatorial regime between the 0.5° and 0.25° model versions, with both solutions capturing the observed SST variability in the Niño3-region. The question of remotely forced oceanic contributions to the equatorial variability, in particular, the role of low-frequency changes in the transports of the Subtropical Cells (STCs), is addressed by a sequence of perturbation experiments using different combinations of fluxes. The solutions show the near-surface temperature variability to be governed by wind-driven changes in the Equatorial Undercurrent. The relative contributions of equatorial and off-equatorial atmospheric forcing differ between interannual and longer, (multi-) decadal timescales: for the latter there is a significant impact of changes in the equatorward transport of subtropical thermocline water associated with the lower branches of the STCs, related to variations in the off-equatorial trade winds. A conspicuous feature of the STC variability is that the equatorward transports in the interior and along the western boundary partially compensate each other at both decadal and interannual time scales, with the strongest transport extrema occurring during El Niño episodes. The behaviour is rationalized in terms of a wobbling in the poleward extents of the tropical gyres, which is manifested also in a meridional shifting of the bifurcation latitudes of the North and South Equatorial Current systems.

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

Description: The first three Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Campaigns at Eureka (80° N, 86° W) were during two extremes of Arctic winter variability: Stratospheric sudden warmings (SSWs) in 2004 and 2006 were among the strongest, most prolonged on record; 2005 was a record cold winter. New satellite measurements from ACE-Fourier Transform Spectrometer (ACE-FTS), Sounding of the Atmosphere using Broadband Emission Radiometry, and Aura Microwave Limb Sounder (MLS), with meteorological analyses and Eureka lidar and radiosonde temperatures, are used to detail the meteorology in these winters, to demonstrate its influence on transport and chemistry, and to provide a context for interpretation of campaign observations. During the 2004 and 2006 SSWs, the vortex broke down throughout the stratosphere, reformed quickly in the upper stratosphere, and remained weak in the middle and lower stratosphere. The stratopause reformed at very high altitude, above where it could be accurately represented in the meteorological analyses. The 2004 and 2006 Eureka campaigns were during the recovery from the SSWs, with the redeveloping vortex over Eureka. 2005 was the coldest winter on record in the lower stratosphere, but with an early final warming in mid-March. The vortex was over Eureka at the start of the 2005 campaign, but moved away as it broke up. Disparate temperature profile structure and vortex evolution resulted in much lower (higher) temperatures in the upper (lower) stratosphere in 2004 and 2006 than in 2005. Satellite temperatures agree well with Eureka radiosondes, and with lidar data up to 50–60 km. Consistent with a strong, cold upper stratospheric vortex and enhanced radiative cooling after the SSWs, MLS and ACE-FTS trace gas measurements show strongly enhanced descent in the upper stratospheric vortex during the 2004 and 2006 Eureka campaigns compared to that in 2005.

Description: The accurate reconstruction of sea surface temperature (SST) history in climate-sensitive regions (e.g. tropical and polar oceans) became a challenging task in palaeoceanographic research. Biogenic shell carbonate SST proxies successfully developed for tropical regions often fail in cool water environments. Their major regional shortcomings and the cryptic diversity now found within the major high latitude proxy carrier Neogloboquadrina pachyderma (sin.) highlight an urgent need to explore complementary SST proxies for these cool-water regions. Here we incorporate the genetic component into a calibration study of a new SST proxy for the high latitudes. We found that the calcium isotopic composition (δ44/40Ca) of calcite from genotyped net catches and core-top samples of the planktonic foraminifera Neogloboquadrina pachyderma (sin.) is related to temperature and unaffected by genetic variations. The temperature sensitivity has been found to be 0.17 (±0.02)‰ per 1°C, highlighting its potential for downcore applications in open marine cool-water environments. Our results further indicate that in extreme polar environments, below a critical threshold temperature of 2.0 (±0.5)°C associated with salinities below 33.0 (±0.5)‰, a prominent shift in biomineralization affects the δ44/40Ca of genotyped and core-top N. pachyderma (sin.), becoming insensitive to temperature. These findings highlight the need of more systematic calibration studies on single planktonic foraminiferal species in order to unravel species-specific factors influencing the temperature sensitivity of Ca isotope fractionation and to validate the proxies' applicability.

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

Description: Rates of dinitrogen (N2) fixation and primary production were measured during two 9 day transect cruises in the Baltic proper in June–July of 1998 and 1999. Assuming that the early phase of the bloom of cyanobacteria lasted a month, total rates of N2 fixation contributed 15 mmol N m−2 (1998) and 33 mmol N m−2 (1999) to new production (sensu Dugdale and Goering, 1967). This constitutes 12–26% more new N than other annual estimates (mid July–mid October) from the same region. The between-station variability observed in both total N2 fixation and primary productivity greatly emphasizes the need for multiple stations and seasonal sampling strategies in biogeochemical studies of the Baltic Sea. The majority of new N from N2 fixation was contributed by filamentous cyanobacteria. On average, cyanobacterial cells 〉20 µm were able to supply a major part of their N requirements for growth by N2 fixation in both 1998 (73%) and 1999 (81%). The between-station variability was high however, and ranged from 28–150% of N needed to meet the rate of C incorporation by primary production. The molar C:N rate incorporation ratio (C:NRATE) in filamentous cyanobacterial cells was variable (range 7–28) and the average almost twice as high as the Redfield ratio (6.6) in both years. Since the molar C:N mass ratio (C:NMASS) in filamentous cyanobacterial cells was generally lower than C:NRATE at a number of stations, we suggest that the diazotrophs incorporated excess C on a short term basis (carbohydrate ballasting and buoyancy regulation), released nitrogen or utilized other regenerated sources of N nutrients. Measured rates of total N2 fixation contributed only a minor fraction of 13% (range 4–24) in 1998 and 18% (range 2–45) in 1999 to the amount of N needed for the community primary production. An average of 9 and 15% of total N2 fixation was found in cells 〈5 µm. Since cells 〈5 µm did not show any detectable rates of N2 fixation, the 15N-enrichment could be attributed to regenerated incorporation of dissolved organic N (DON) and ammonium generated from larger diazotroph cyanobacteria. Therefore, N excretion from filamentous cyanobacteria may significantly contribute to the pool of regenerated nutrients used by the non-diazotroph community in summer. Higher average concentrations of regenerated N (ammonium) coincided with higher rates of N2 fixation found during the 1999 transect and a higher level of 15N-enrichment in cells 〈5 µm. A variable but significant fraction of total N2 fixation (1–10%) could be attributed to diazotrophy in cells between 5–20 µm.

Description: Water column data of carbon and carbon relevant hydrographic and hydrochemical parameters from 188 previously non-publicly available cruises in the Arctic, Atlantic, and Southern Ocean have been retrieved and merged into a new database: CARINA (CARbon IN the Atlantic). The data have been subject to rigorous quality control (QC) in order to ensure highest possible quality and consistency. The data for most of the parameters included were examined in order to quantify systematic biases in the reported values, i.e. secondary quality control. Significant biases have been corrected for in the data products, i.e. the three merged files with measured, calculated and interpolated values for each of the three CARINA regions; the Arctic Mediterranean Seas (AMS), the Atlantic (ATL) and the Southern Ocean (SO). With the adjustments the CARINA database is consistent both internally as well as with GLODAP (Key et al., 2004) and is suitable for accurate assessments of, for example, oceanic carbon inventories and uptake rates and for model validation. The Arctic Mediterranean Seas include the Arctic Ocean and the Nordic Seas, and the quality control was carried out separately in these two areas. This contribution provides an overview of the CARINA data from the Nordic Seas and summarises the findings of the QC of the salinity data. One cruise had salinity data that were of questionable quality, and these have been removed from the data product. An evaluation of the consistency of the quality controlled salinity data suggests that they are consistent to at least ±0.005.

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: Dedicated to the memory of our colleague Klaus Hochheim, who tragically lost his life in the Arctic expedition in September 2013. A distinct, subsurface density front along the eastern St. Anna Trough in the northern Kara Sea is inferred from hydrographic observations in 1996 and 2008–2010. Direct velocity measurements show a persistent northward subsurface current (~ 18 cm s−1) along the St. Anna Trough eastern flank. This sheared flow, carrying the outflow from the Barents and Kara seas to the Arctic Ocean, is also evident from shipboard observations as well as from geostrophic velocities and numerical model simulations. Although we cannot substantiate our conclusions by direct observation-based estimates of mixing rates in the area, we hypothesize that the enhanced vertical mixing along the St. Anna Trough eastern flank favors the upward heat loss from the intermediate warm Atlantic water layer. Modeling results support this hypothesis. The upward heat flux inferred from hydrographic data and model simulations is of O(30–100) W m−2. The region of lowered sea ice thickness and concentration seen both in sea ice remote sensing observations and model simulations marks the Atlantic water pathway in the St. Anna Trough and adjacent Nansen Basin continental margin. In fact, the sea ice shows a delayed freeze-up onset during fall and a reduction in the sea ice thickness during winter. This is consistent with our results on the enhanced Atlantic water heat loss along the Atlantic water pathway in the St. Anna Trough.

Description: Following the launch of ESA's Soil Moisture and Ocean Salinity (SMOS) mission, it has been shown that brightness temperatures at a low microwave frequency of 1.4 GHz (L-band) are sensitive to sea ice properties. In the first demonstration study, sea ice thickness up to 50 cm has been derived using a semi-empirical algorithm with constant tie-points. Here, we introduce a novel iterative retrieval algorithm that is based on a thermodynamic sea ice model and a three-layer radiative transfer model, which explicitly takes variations of ice temperature and ice salinity into account. In addition, ice thickness variations within the SMOS spatial resolution are considered through a statistical thickness distribution function derived from high-resolution ice thickness measurements from NASA's Operation IceBridge campaign. This new algorithm has been used for the continuous operational production of a SMOS-based sea ice thickness data set from 2010 on. The data set is compared to and validated with estimates from assimilation systems, remote sensing data, and airborne electromagnetic sounding data. The comparisons show that the new retrieval algorithm has a considerably better agreement with the validation data and delivers a more realistic Arctic-wide ice thickness distribution than the algorithm used in the previous study (Kaleschke et al., 2012).

Description: Samoylov Island is centrally located within the Lena River Delta at 72° N, 126° E and lies within the Siberian zone of continuous permafrost. The landscape on Samoylov Island consists mainly of late Holocene river terraces with polygonal tundra, ponds and lakes, and an active floodplain. The island has been the focus of numerous multidisciplinary studies since 1993, which have focused on climate, land cover, ecology, hydrology, permafrost and limnology. This paper aims to provide a framework for future studies by describing the characteristics of the island's meteorological parameters (temperature, radiation and snow cover), soil temperature, and soil moisture. The land surface characteristics have been described using high resolution aerial images in combination with data from ground-based observations. Of note is that deeper permafrost temperatures have increased between 0.3 to 1.3 °C over the last five years. However, no clear warming of air and active layer temperatures is detected since 1998, though winter air temperatures during recent years have not been as cold as in earlier years.

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: Advances in detector technology enable a new generation of infrared limb sounders to measure 2-D images of the atmosphere. A proposed limb cloud imager (LCI) mode will detect clouds with a spatial resolution unprecedented for limb sounding. For the inference of temperature and trace gas distributions, detector pixels of the LCI have to be combined into super-pixels which provide the required signal-to-noise and information content for the retrievals. This study examines the extent to which tropospheric coverage can be improved in comparison to limb sounding using a fixed field of view with the size of the super-pixels, as in conventional limb sounders. The study is based on cloud topographies derived from (a) IR brightness temperatures (BT) of geostationary weather satellites in conjunction with ECMWF temperature profiles and (b) ice and liquid water content data of the Consortium for Small-scale Modeling-Europe (COSMO-EU) of the German Weather Service. Limb cloud images are simulated by matching the cloud topography with the limb sounding line of sight (LOS). The analysis of the BT data shows that the reduction of the spatial sampling along the track has hardly any effect on the gain in information. The comparison between BT and COSMO-EU data identifies the strength of both data sets, which are the representation of the horizontal cloud extent for the BT data and the reproduction of the cloud amount for the COSMO-EU data. The results of the analysis of both data sets show the great advantage of the cloud imager. However, because both cloud data sets do not present the complete fine structure of the real cloud fields in the atmosphere it is assumed that the results tend to underestimate the increase in information. In conclusion, real measurements by such an instrument may result in an even higher benefit for tropospheric limb retrievals.

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: In early May 2006 a record high air pollution event was observed at Ny-Ålesund, Spitsbergen. An atypical weather pattern established a pathway for the rapid transport of biomass burning aerosols from agricultural fires in Eastern Europe to the Arctic. Atmospheric stability was such that the smoke was constrained to low levels, within 2 km of the surface during the transport. A description of this smoke event in terms of transport and main aerosol characteristics can be found in Stohl et al. (2007). This study puts emphasis on the radiative effect of the smoke. The aerosol number size distribution was characterised by lognormal parameters as having an accumulation mode centered around 165–185 nm and almost 1.6 for geometric standard deviation of the mode. Nucleation and small Aitken mode particles were almost completely suppressed within the smoke plume measured at Ny-Ålesund. Chemical and microphysical aerosol information obtained at Mt. Zeppelin (474 m a.s.l) was used to derive input parameters for a one-dimensional radiation transfer model to explore the radiative effects of the smoke. The daily mean heating rate calculated on 2 May 2006 for the average size distribution and measured chemical composition reached 0.55 K day−1 at 0.5 km altitude for the assumed external mixture of the aerosols but showing much higher heating rates for an internal mixture (1.7 K day−1). In comparison a case study for March 2000 showed that the local climatic effects due to Arctic haze, using a regional climate model, HIRHAM, amounts to a maximum of 0.3 K day−1 of heating at 2 km altitude (Treffeisen et al., 2005).

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: In recent decades, the central North Sea has been experiencing a general trend of decreasing dissolved oxygen (O2) levels during summer. To understand potential causes driving lower O2, we investigated a 3-day period of summertime turbulence and O2 dynamics in the thermocline and bottom boundary layer (BBL). The study focuses on coupling biogeochemical with physical transport processes to identify key drivers of the O2 and organic carbon turnover within the BBL. Combining our flux observations with an analytical process-oriented approach, we resolve drivers that ultimately contribute to determining the BBL O2 levels. We report substantial turbulent O2 fluxes from the thermocline into the otherwise isolated bottom water attributed to the presence of a baroclinic near-inertial wave. This contribution to the local bottom water O2 and carbon budgets has been largely overlooked and is shown to play a role in promoting high carbon turnover in the bottom water while simultaneously maintaining high O2 concentrations. This process may become suppressed with warming climate and stronger stratification, conditions which could promote migrating algal species that potentially shift the O2 production zone higher up within the thermocline.

Description: The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high-volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition, including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa, with the latter often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5-year PM10 mean was 47.1 ± 55.5 μg m−2, while the mineral dust and sea salt means were 27.9 ± 48.7 and 11.1 ± 5.5 μg m−2, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long-range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 ± 0.6 μg m−3, the aerosol mass, OC (organic carbon) and EC (elemental carbon), showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods when air mass inflow was predominantly of marine origin, indicating that marine biogenic emissions were a significant source. Ammonium showed a distinct maximum in spring and coincided with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons, indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion, differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 ± 8.5% (62 ± 42%) in Saharan-dust-dominated air mass to 30 \textpm 12% (87 ± 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer; while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. Positive matrix factorization (PMF) analysis identified three major aerosol sources: sea salt, aged sea salt and long-range transport. The ionic budget was dominated by the first two of these factors, while the long-range transport factor could only account for about 14% of the total observed ionic mass.

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: During a cruise of R/V METEOR in December 2012 the oceanic sources and emissions of various halogenated trace gases and their mixing ratios in the marine atmospheric boundary layer (MABL) were investigated above the Peruvian upwelling. This study presents novel observations of the three very short lived substances (VSLSs) – bromoform, dibromomethane and methyl iodide – together with high-resolution meteorological measurements, Lagrangian transport and source–loss calculations. Oceanic emissions of bromoform and dibromomethane were relatively low compared to other upwelling regions, while those for methyl iodide were very high. Radiosonde launches during the cruise revealed a low, stable MABL and a distinct trade inversion above acting as strong barriers for convection and vertical transport of trace gases in this region. Observed atmospheric VSLS abundances, sea surface temperature, relative humidity and MABL height correlated well during the cruise. We used a simple source–loss estimate to quantify the contribution of oceanic emissions along the cruise track to the observed atmospheric concentrations. This analysis showed that averaged, instantaneous emissions could not support the observed atmospheric mixing ratios of VSLSs and that the marine background abundances below the trade inversion were significantly influenced by advection of regional sources. Adding to this background, the observed maximum emissions of halocarbons in the coastal upwelling could explain the high atmospheric VSLS concentrations in combination with their accumulation under the distinct MABL and trade inversions. Stronger emissions along the nearshore coastline likely added to the elevated abundances under the steady atmospheric conditions. This study underscores the importance of oceanic upwelling and trade wind systems on the atmospheric distribution of marine VSLS emissions.

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 fixation by filamentous cyanobacteria supplies significant amounts of new nitrogen (N) to the Baltic Sea. This balances N loss processes such as denitrification and anammox and forms an important N source supporting primary and secondary production in N-limited post-spring bloom plankton communities. Laboratory studies suggest that filamentous diazotrophic cyanobacteria growth and N2-fixation rates are sensitive to ocean acidification with potential implications for new N supply to the Baltic Sea. In this study, our aim was to assess the effect of ocean acidification on diazotroph growth and activity as well as the contribution of diazotrophically-fixed N to N supply in a natural plankton assemblage. We enclosed a natural plankton community in a summer season in the Baltic Sea near the entrance to the Gulf of Finland in six large-scale mesocosms (volume ~ 55 m3) and manipulated fCO2 over a range relevant for projected ocean acidification by the end of this century (average treatment fCO2: 365–1231 μatm). The direct response of diazotroph growth and activity was followed in the mesocosms over a 47 day study period during N-limited growth in the summer plankton community. Diazotrophic filamentous cyanobacteria abundance throughout the study period and N2-fixation rates (determined only until day 21 due to subsequent use of contaminated commercial 15N-N2 gas stocks) remained low. Thus estimated new N inputs from diazotrophy were too low to relieve N limitation and stimulate a summer phytoplankton bloom. Instead regeneration of organic N sources likely sustained growth in the plankton community. We could not detect significant CO2-related differences in inorganic or organic N pools sizes, or particulate matter N : P stoichiometry. Additionally, no significant effect of elevated CO2 on diazotroph activity was observed. Therefore, ocean acidification had no observable impact on N cycling or biogeochemistry in this N-limited, post-spring bloom plankton assemblage in the Baltic Sea.

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: An earth system model of intermediate complexity (CLIMate and BiosphERe – CLIMBER-2) and a land surface model (JSBACH), which dynamically represent vegetation, are used to simulate natural fire dynamics through the last 8000 yr. Output variables of the fire model (burned area and fire carbon emissions) are used to compare model results with sediment-based charcoal reconstructions. Several approaches for processing model output are also tested. Charcoal data are reported in Z-scores with a base period of 8000–200 BP in order to exclude the strong anthropogenic forcing of fire during the last two centuries. The model–data comparison reveals a robust correspondence in fire activity for most regions considered, while for a few regions, such as Europe, simulated and observed fire histories show different trends. The difference between modelled and observed fire activity may be due to the absence of anthropogenic forcing (e.g. human ignitions and suppression) in the model simulations, and also due to limitations inherent to modelling fire dynamics. The use of spatial averaging (or Z-score processing) of model output did not change the directions of the trends. However, Z-score-transformed model output resulted in higher rank correlations with the charcoal Z-scores in most regions. Therefore, while both metrics are useful, processing model output as Z-scores is preferable to areal averaging when comparing model results to transformed charcoal records.

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: The coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4° S, and 82.0 to 77.5° W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation–emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 nm−1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15° S. By EEMs, we identified five fluorescent components (F1–5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m−1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air–sea gas exchange in this area.

Description: Community approaches to investigating ocean acidification (OA) effects suggest a high tolerance of micro- and mesozooplankton to carbonate chemistry changes expected to occur within this century. Plankton communities in the coastal areas of the Baltic Sea frequently experience pH variations partly exceeding projections for the near future both on a diurnal and seasonal basis. We conducted a large-scale mesocosm CO2 enrichment experiment ( ∼  55 m3) enclosing the natural plankton community in Tvärminne–Storfjärden for 8 weeks during June–August 2012 and studied community and species–taxon response of ciliates and mesozooplankton to CO2 elevations expected for this century. In addition to the response to fCO2, we also considered temperature and chlorophyll a variations in our analyses. Shannon diversity of ciliates significantly decreased with fCO2 and temperature with a greater dominance of smaller species. The mixotrophic Myrionecta rubra seemed to indirectly and directly benefit from higher CO2 concentrations in the post-bloom phase through increased occurrence of picoeukaryotes (most likely Cryptophytes) and Dinophyta at higher CO2 levels. With respect to mesozooplankton, we did not detect significant effects for either total abundance or for Shannon diversity. The cladocera Bosmina sp. occurred at distinctly higher abundance for a short time period during the second half of the experiment in three of the CO2-enriched mesocosms except for the highest CO2 level. The ratio of Bosmina sp. with empty to embryo- or resting-egg-bearing brood chambers, however, was significantly affected by CO2, temperature, and chlorophyll a. An indirect CO2 effect via increased food availability (Cyanobacteria) stimulating Bosmina sp. reproduction cannot be ruled out. Although increased regenerated primary production diminishes trophic transfer in general, the presence of organisms able to graze on bacteria such as cladocerans may positively impact organic matter transfer to higher trophic levels. Thus, under increasing OA in cladoceran-dominated mesozooplankton communities, the importance of the microbial loop in the pelagic zone may be temporarily enhanced and carbon transfer to higher trophic levels may be stimulated.

Description: Bulk aerosol samples collected during cruise M91 of FS Meteor off the coast of Peru in December 2012 were analysed for their soluble trace metal (Fe, Al, Mn, Ti, Zn, V, Ni, Cu, Co, Cd, Pb, Th) and major ion (including NO3− and NH4+) content. These data are among the first recorded for trace metals in this relatively poorly studied region of the global marine atmosphere. To the north of ∼ 13° S, the concentrations of several elements (Fe, Ti, Zn, V, Ni, Pb) appear to be related to distance from the coast. At the south of the transect (∼ 15–16° S), elevated concentrations of Fe, Cu, Co and Ni were observed. These may be related to the activities of the large smelting facilities in the south of Peru or northern Chile. Calculated dry deposition fluxes (3370–17 800 and 16–107 nmol m−2 d−1 for inorganic nitrogen and soluble Fe respectively) indicated that atmospheric input to the waters of the Peru upwelling system contains an excess of Fe over N, with respect to phytoplankton requirements. This may be significant as primary production in these waters has been reported to be limited by Fe availability, but atmospheric deposition is unlikely to be the dominant source of Fe to the system

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: Anthropogenic carbon dioxide (CO2) emissions are causing severe changes in the global inorganic carbon balance of the oceans. Associated ocean acidification is expected to impose a major threat to marine ecosystems worldwide, and it is also expected to be amplified in the Baltic Sea where the system is already at present exposed to relatively large natural seasonal and diel pH fluctuations. The response of organisms to future ocean acidification has primarily been studied in single-species experiments, whereas the knowledge of community-wide responses is still limited. To study responses of the Baltic Sea pelagic community to a range of future CO2-scenarios, six ∼ 55 m3 pelagic mesocosms were deployed in the northern Baltic Sea in June 2012. In this specific study we focused on the tolerance, development and subsequent settlement process of the larvae of the benthic key-species Macoma balthica when exposed to different levels of future CO2. We found that the settling of M. balthica was delayed along the increasing CO2 gradient of the mesocosms. Also, when exposed to increasing CO2 levels larvae settled at a larger size, indicating a developmental delay. With on-going climate change, both the frequency and extent of regularly occurring high CO2 conditions is likely to increase, and a permanent pH decrease will likely occur. The strong impact of increasing CO2 levels on early-stage bivalves is alarming as these stages are crucial for sustaining viable populations, and a failure in their recruitment would ultimately lead to negative effects on the population.

Description: The satellite-derived HOAPS (Hamburg Ocean Atmosphere Parameters and Fluxes from Satellite Data) and ECMWF (European Centre for Medium-Range Weather Forecasts) ERA-Interim reanalysis data sets have been validated against in situ precipitation measurements from ship rain gauges and optical disdrometers over the open ocean by applying a statistical analysis for binary estimates. For this purpose collocated pairs of data were merged within a certain temporal and spatial threshold into single events, according to the satellites' overpass, the observation and the ERA-Interim times. HOAPS detects the frequency of precipitation well, while ERA-Interim strongly overestimates it, especially in the tropics and subtropics. Although precipitation rates are difficult to compare because along-track point measurements are collocated with areal estimates and the number of available data are limited, we find that HOAPS underestimates precipitation rates, while ERA-Interim's Atlantic-wide average precipitation rate is close to measurements. However, when regionally averaged over latitudinal belts, deviations between the observed mean precipitation rates and ERA-Interim exist. The most obvious ERA-Interim feature is an overestimation of precipitation in the area of the intertropical convergence zone and the southern subtropics over the Atlantic Ocean. For a limited number of snow measurements by optical disdrometers, it can be concluded that both HOAPS and ERA-Interim are suitable for detecting the occurrence of solid precipitation.

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

Description: Ocean deoxygenation due to climate change may alter redox-sensitive nutrient cycles in the marine environment. The productive eastern tropical North Atlantic (ETNA) upwelling region may be particularly affected when the relatively moderate oxygen minimum zone (OMZ) deoxygenates further and microbially driven nitrogen (N) loss processes are promoted. Consequently, water masses with a low nitrogen to phosphorus (N : P) ratio could reach the euphotic layer, possibly influencing primary production in those waters. Previous mesocosm studies in the oligotrophic Atlantic Ocean identified nitrate availability as a control of primary production, while a possible co-limitation of nitrate and phosphate could not be ruled out. To better understand the impact of changing N : P ratios on primary production and N2 fixation in the ETNA surface ocean, we conducted land-based mesocosm experiments with natural plankton communities and applied a broad range of N : P ratios (2.67–48). Silicic acid was supplied at 15 µmol L−1 in all mesocosms. We monitored nutrient drawdown, biomass accumulation and nitrogen fixation in response to variable nutrient stoichiometry. Our results confirmed nitrate to be the key factor determining primary production. We found that excess phosphate was channeled through particulate organic matter (POP) into the dissolved organic matter (DOP) pool. In mesocosms with low inorganic phosphate availability, DOP was utilized while N2 fixation increased, suggesting a link between those two processes. Interestingly this observation was most pronounced in mesocosms where nitrate was still available, indicating that bioavailable N does not necessarily suppress N2 fixation. We observed a shift from a mixed cyanobacteria–proteobacteria dominated active diazotrophic community towards a diatom-diazotrophic association of the Richelia-Rhizosolenia symbiosis. We hypothesize that a potential change in nutrient stoichiometry in the ETNA might lead to a general shift within the diazotrophic community, potentially influencing primary productivity and carbon export.

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: The storage of anthropogenic carbon in the ocean's interior is an important process which modulates the increasing carbon dioxide concentrations in the atmosphere. The polar regions are expected to be net sinks for anthropogenic carbon. Transport estimates of dissolved inorganic carbon and the anthropogenic offset can thus provide information about the magnitude of the corresponding storage processes. Here we present a transient tracer, dissolved inorganic carbon (DIC) and total alkalinity (TA) data set along 78°50′ N sampled in the Fram Strait in 2012. A theory on tracer relationships is introduced, which allows for an application of the inverse-Gaussian–transit-time distribution (IG-TTD) at high latitudes and the estimation of anthropogenic carbon concentrations. Mean current velocity measurements along the same section from 2002–2010 were used to estimate the net flux of DIC and anthropogenic carbon by the boundary currents above 840 m through the Fram Strait. The new theory explains the differences between the theoretical (IG-TTD-based) tracer age relationship and the specific tracer age relationship of the field data, by saturation effects during water mass formation and/or the deliberate release experiment of SF6 in the Greenland Sea in 1996, rather than by different mixing or ventilation processes. Based on this assumption, a maximum SF6 excess of 0.5–0.8 fmol kg−1 was determined in the Fram Strait at intermediate depths (500–1600 m). The anthropogenic carbon concentrations are 50–55 µmol kg−1 in the Atlantic Water/Recirculating Atlantic Water, 40–45 µmol kg−1 in the Polar Surface Water/warm Polar Surface Water and between 10 and 35 µmol kg−1 in the deeper water layers, with lowest concentrations in the bottom layer. The net fluxes through the Fram Strait indicate a net outflow of  ∼  0.4 DIC and  ∼  0.01 PgC yr−1 anthropogenic carbon from the Arctic Ocean into the North Atlantic, albeit with high uncertainties.

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: The eastern tropical North Atlantic (ETNA) features a mesopelagic oxygen minimum zone (OMZ) at approximately 300–600 m depth. Here, oxygen concentrations rarely fall below 40 µmol O2 kg−1, but are expected to decline under future projections of global warming. The recent discovery of mesoscale eddies that harbour a shallow suboxic (〈 5 µmol O2 kg−1) OMZ just below the mixed layer could serve to identify zooplankton groups that may be negatively or positively affected by ongoing ocean deoxygenation. In spring 2014, a detailed survey of a suboxic anticyclonic modewater eddy (ACME) was carried out near the Cape Verde Ocean Observatory (CVOO), combining acoustic and optical profiling methods with stratified multinet hauls and hydrography. The multinet data revealed that the eddy was characterized by an approximately 1.5-fold increase in total area-integrated zooplankton abundance. At nighttime, when a large proportion of acoustic scatterers is ascending into the upper 150 m, a drastic reduction in mean volume backscattering (Sv) at 75 kHz (shipboard acoustic Doppler current profiler, ADCP) within the shallow OMZ of the eddy was evident compared to the nighttime distribution outside the eddy. Acoustic scatterers avoided the depth range between approximately 85 to 120 m, where oxygen concentrations were lower than approximately 20 µmol O2 kg−1, indicating habitat compression to the oxygenated surface layer. This observation is confirmed by time series observations of a moored ADCP (upward looking, 300 kHz) during an ACME transit at the CVOO mooring in 2010. Nevertheless, part of the diurnal vertical migration (DVM) from the surface layer to the mesopelagic continued through the shallow OMZ. Based upon vertically stratified multinet hauls, Underwater Vision Profiler (UVP5) and ADCP data, four strategies followed by zooplankton in response to in response to the eddy OMZ have been identified: (i) shallow OMZ avoidance and compression at the surface (e.g. most calanoid copepods, euphausiids); (ii) migration to the shallow OMZ core during daytime, but paying O2 debt at the surface at nighttime (e.g. siphonophores, Oncaea spp., eucalanoid copepods); (iii) residing in the shallow OMZ day and night (e.g. ostracods, polychaetes); and (iv) DVM through the shallow OMZ from deeper oxygenated depths to the surface and back. For strategy (i), (ii) and (iv), compression of the habitable volume in the surface may increase prey–predator encounter rates, rendering zooplankton and micronekton more vulnerable to predation and potentially making the eddy surface a foraging hotspot for higher trophic levels. With respect to long-term effects of ocean deoxygenation, we expect avoidance of the mesopelagic OMZ to set in if oxygen levels decline below approximately 20 µmol O2 kg−1. This may result in a positive feedback on the OMZ oxygen consumption rates, since zooplankton and micronekton respiration within the OMZ as well as active flux of dissolved and particulate organic matter into the OMZ will decline.

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 occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40–100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, underwater gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg−1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0–70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg−1 day−1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m−2 day−1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.

Description: The Baltic and Black Seas are both brackish, that is to say both have salinities intermediate between freshwater and seawater. The coccolithophore Emiliania huxleyi is abundant in one, the Black Sea, but absent from the other, the Baltic Sea. Here we present summertime coccolithophore measurements confirming this difference, as well as data on the calcium carbonate saturation state of the Baltic Sea. We find that the Baltic Sea becomes undersaturated (or nearly so) in winter, with respect to both the aragonite and calcite mineral forms of CaCO3. Data for the Black Sea are more limited, but it appears to remain strongly supersaturated year-round. The absence of E. huxleyi from the Baltic Sea could therefore potentially be explained by dissolution of their coccoliths in winter, suggesting that minimum annual (wintertime) saturation states could be most important in determining future ocean acidification impacts. In addition to this potential importance of winter saturation state, alternative explanations are also possible, either related to differences in salinity or else to differences in silicate concentrations.

Description: Satellite observations of microwave brightness temperatures between 19 GHz and 85 GHz are the main data sources for operational sea-ice monitoring and retrieval of ice concentrations. However, microwave brightness temperatures depend on the emissivity of snow and ice, which is subject to pronounced seasonal variations and shows significant hemispheric contrasts. These mainly arise from differences in the rate and strength of snow metamorphism and melt. We here use the thermodynamic snow model SNTHERM forced by European Re-Analysis (ERA) interim data and the Microwave Emission Model of Layered Snowpacks (MEMLS), to calculate the sea-ice surface emissivity and to identify the contribution of regional patterns in atmospheric conditions to its variability in the Arctic and Antarctic. The computed emissivities reveal a pronounced seasonal cycle with large regional variability. The emissivity variability increases from winter to early summer and is more pronounced in the Antarctic. In the pre-melt period (January–May, July–November) the standard deviations in surface microwave emissivity due to diurnal, regional and inter-annual variability of atmospheric forcing reach up to Δε = 0.034, 0.043, and 0.097 for 19 GHz, 37 GHz and 85 GHz channels, respectively. Between 2000 and 2009, small but significant positive emissivity trends were observed in the Weddell Sea during November and December as well as in Fram Strait during February, potentially related to earlier melt onset in these regions. The obtained results contribute to a better understanding of the uncertainty and variability of sea-ice concentration and snow-depth retrievals in regions of high sea-ice concentrations.

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

Description: Artificial Neural Networks (ANN) are efficient tools to derive solar UV radiation from measured meteorological parameters such as global radiation, aerosol optical depths and atmospheric column ozone. The ANN model has been tested with different combinations of data from the two sites Potsdam and Lindenberg, and used to reconstruct solar UV radiation at eight European sites by more than 100 years into the past. Special emphasis will be given to the discussion of small-scale characteristics of input data to the ANN model. Annual totals of UV radiation derived from reconstructed daily UV values reflect interannual variations and long-term patterns that are compatible with variabilities and changes of measured input data, in particular global dimming by about 1980/1990, subsequent global brightening, volcanic eruption effects such as that of Mt. Pinatubo, and the long-term ozone decline since the 1970s. Patterns of annual erythemal UV radiation are very similar at sites located at latitudes close to each other, but different patterns occur between UV radiation at sites in different latitude regions.

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: The sea-surface microlayer (SML) is at the uppermost surface of the ocean, linking the hydrosphere with the atmosphere. The presence and enrichment of organic compounds in the SML have been suggested to influence air–sea gas exchange processes as well as the emission of primary organic aerosols. Here, we report on organic matter components collected from an approximately 50 µm thick SML and from the underlying water (ULW),  ∼  20 cm below the SML, in December 2012 during the SOPRAN METEOR 91 cruise to the highly productive, coastal upwelling regime off the coast of Peru. Samples were collected at 37 stations including coastal upwelling sites and off-shore stations with less organic matter and were analyzed for total and dissolved high molecular weight (〉 1 kDa) combined carbohydrates (TCCHO, DCCHO), free amino acids (FAA), total and dissolved hydrolyzable amino acids (THAA, DHAA), transparent exopolymer particles (TEP), Coomassie stainable particles (CSPs), total and dissolved organic carbon (TOC, DOC), total and dissolved nitrogen (TN, TDN), as well as bacterial and phytoplankton abundance. Our results showed a close coupling between organic matter concentrations in the water column and in the SML for almost all components except for FAA and DHAA that showed highest enrichment in the SML on average. Accumulation of gel particles (i.e., TEP and CSP) in the SML differed spatially. While CSP abundance in the SML was not related to wind speed, TEP abundance decreased with wind speed, leading to a depletion of TEP in the SML at about 5 m s−1. Our study provides insight to the physical and biological control of organic matter enrichment in the SML, and discusses the potential role of organic matter in the SML for air–sea exchange processes.

Description: Emissions of halogenated very short lived substances (VSLS) from the tropical oceans contribute to the atmospheric halogen budget and affect tropospheric and stratospheric ozone. Here we investigate the contribution of natural oceanic VSLS emissions to the Marine Atmospheric Boundary Layer (MABL) and their transport into the Free Troposphere (FT) over the tropical West Pacific. The study concentrates in particular on ship and aircraft measurements of the VSLS bromoform, dibromomethane and methyl iodide and meteorological parameters during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) campaign in the South China and Sulu Seas in November 2011. Elevated oceanic concentrations of 19.9 (2.80–136.91) pmol L−1 for bromoform, 5.0 (2.43–21.82) pmol L−1 for dibromomethane and 3.8 (0.55–18.83) pmol L−1 for methyl iodide in particular close to Singapore and at the coast of Borneo with high corresponding oceanic emissions of 1486 ± 1718 pmol m−2 h−1 for bromoform, 405 ± 349 pmol m−2 h−1 for dibromomethane and 433 ± 482 pmol m−2 h−1 for methyl iodide characterize this tropical region as a strong source of these compounds. Unexpectedly atmospheric mixing ratios in the MABL were relatively low with 2.08 ± 2.08 ppt for bromoform, 1.17 ± 1.17 ppt for dibromomethane and 0.39 ± 0.09 ppt for methyl iodide. We use meteorological and chemical ship and aircraft observations, FLEXPART trajectory calculations and source-loss estimates to identify the oceanic VSLS contribution to the MABL and to the FT. Our results show that a convective, well-ventilated MABL and intense convection led to the low atmospheric mixing ratios in the MABL despite the high oceanic emissions in coastal areas of the South-China and Sulu Seas. While the accumulated bromoform in the FT above the region origins almost entirely from the local South China Sea area, dibromomethane is largely advected from distant source regions. The accumulated FT mixing ratio of methyl iodide is higher than can be explained with the local oceanic or MABL contributions. Possible reasons, uncertainties and consequences of our observations and model estimates are discussed.

Description: Benthic nitrogen (N2) fixation and sulfate reduction (SR) were investigated in the Peruvian oxygen minimum zone (OMZ). Sediment samples, retrieved by a multiple corer were taken at six stations (70–1025 m) along a depth transect at 12° S, covering anoxic and hypoxic bottom water conditions. Benthic N2 fixation was detected at all sites, with high rates measured in OMZ mid-waters between the 70 and 253 m and lowest N2 fixation rates below 253 m down to 1025 m water depth. SR rates were decreasing with increasing water depth, with highest rates at the shallow site. Benthic N2 fixation depth profiles largely overlapped with SR depth profiles, suggesting that both processes are coupled. The potential of N2 fixation by SR bacteria was verified by the molecular analysis of nifH genes. Detected nifH sequences clustered with SR bacteria that have been demonstrated to fix N2 in other benthic environments. Depth-integrated rates of N2 fixation and SR showed no direct correlation along the 12° S transect, suggesting that the benthic diazotrophs in the Peruvian OMZ are being controlled by additional various environmental factors. The organic matter availability and the presence of sulfide appear to be major drivers for benthic diazotrophy. It was further found that N2 fixation was not inhibited by high ammonium concentrations. N2 fixation rates in OMZ sediments were similar to rates measured in other organic-rich sediments. Overall, this work improves our knowledge on N sources in marine sediments and contributes to a better understanding of N cycling in OMZ sediments.

Description: We studied the concurrence of methanogenesis and sulfate reduction in surface sediments (0–25 cm below sea floor, cmbsf) at six stations (70, 145, 253, 407, 770 and 1024 m) along the Peruvian margin (12° S). This oceanographic region is characterized by high carbon export to the seafloor, creating an extensive oxygen minimum zone (OMZ) on the shelf, both factors that could favor surface methanogenesis. Sediments sampled along the depth transect traversed areas of anoxic and oxic conditions in the bottom-near water. Net methane production (batch incubations) and sulfate reduction (35S-sulfate radiotracer incubation) were determined in the upper 0–25 cmbsf of multicorer cores from all stations, while deep hydrogenotrophic methanogenesis (〉 30 cmbsf, 14C-bicarbonate radiotracer incubation) was determined in two gravity cores at selected sites (78 and 407 m). Furthermore, stimulation (methanol addition) and inhibition (molybdate addition) experiments were carried out to investigate the relationship between sulfate reduction and methanogenesis. Highest rates of methanogenesis and sulfate reduction in the surface sediments, integrated over 0–25 cmbsf, were observed on the shelf (70–253 m, 0.06–0.1 and 0.5–4.7 mmol m−2 d−1, respectively), while lowest rates were discovered at the deepest site (1024 m, 0.03 and 0.2 mmol m−2 d−1, respectively). The addition of methanol resulted in significantly higher surface methanogenesis activity, suggesting that the process was mostly based on non-competitive substrates, i.e., substrates not used by sulfate reducers. In the deeper sediment horizons, where competition was probably relieved due to the decline of sulfate, the usage of competitive substrates was confirmed by the detection of hydrogenotrophic activity in the sulfate-depleted zone at the shallow shelf station (70 m). Surface methanogenesis appeared to be correlated to the availability of labile organic matter (C / N ratio) and organic carbon degradation (DIC production), both of which support the supply of methanogenic substrates. A negative correlation of methanogenesis rates with dissolved oxygen in the bottom-near water was not obvious, however, anoxic conditions within the OMZ might be advantageous for methanogenic organisms at the sediment–water interface. Our results revealed a high relevance of surface methanogenesis on the shelf, where the ratio between surface to deep (below sulfate penetration) methanogenic activity ranged between 0.13 and 105. In addition, methane concentration profiles indicate a partial release of surface methane into the water column as well as a partial consumption of methane by anaerobic methane oxidation (AOM) in the surface sediment. The present study suggests that surface methanogenesis might play a greater role in benthic methane budgeting than previously thought, especially for fueling AOM above the sulfate-methane transition zone.

Description: The flux of materials to the deep sea is dominated by larger, organic-rich particles with sinking rates varying between a few meters and several hundred meters per day. Mineral ballast may regulate the transfer of organic matter and other components by determining the sinking rates, e.g. via particle density. We calculated particle sinking rates from mass flux patterns and alkenone measurements applying the results of sediment trap experiments from the Atlantic Ocean. We have indication for higher particle sinking rates in carbonate-dominated production systems when considering both regional and seasonal data. During a summer coccolithophorid bloom in the Cape Blanc coastal upwelling off Mauritania, particle sinking rates reached almost 570 m per day, most probably due the fast sedimentation of densely packed zooplankton fecal pellets, which transport high amounts of organic carbon associated with coccoliths to the deep ocean despite rather low production. During the recurring winter-spring blooms off NW Africa and in opal-rich production systems of the Southern Ocean, sinking rates of larger particles, most probably diatom aggregates, showed a tendency to lower values. However, there is no straightforward relationship between carbonate content and particle sinking rates. This could be due to the unknown composition of carbonate and/or the influence of particle size and shape on sinking rates. It also remains noticeable that the highest sinking rates occurred in dust-rich ocean regions off NW Africa, but this issue deserves further detailed field and laboratory investigations. We obtained increasing sinking rates with depth. By using a seven-compartment biogeochemical model, it was shown that the deep ocean organic carbon flux at a mesotrophic sediment trap site off Cape Blanc can be captured fairly well using seasonal variable particle sinking rates. Our model provides a total organic carbon flux of 0.29 Tg per year down to 3000 m off the NW African upwelling region between 5 and 35° N. Simple parameterisations of remineralisation and sinking rates in such models, however, limit their capability in reproducing the flux variation in the water column.

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: Sediment traps are the most common tool to investigate vertical particle flux in the marine realm. However, the spatial and temporal decoupling between particle formation in the surface ocean and particle collection in sediment traps at depth often handicaps reconciliation of production and sedimentation even within the euphotic zone. Pelagic mesocosms are restricted to the surface ocean, but have the advantage of being closed systems and are therefore ideally suited to studying how processes in natural plankton communities influence particle formation and settling in the ocean's surface. We therefore developed a protocol for efficient sample recovery and processing of quantitatively collected pelagic mesocosm sediment trap samples for biogeochemical analysis. Sedimented material was recovered by pumping it under gentle vacuum through a silicon tube to the sea surface. The particulate matter of these samples was subsequently separated from bulk seawater by passive settling, centrifugation or flocculation with ferric chloride, and we discuss the advantages and efficiencies of each approach. After concentration, samples were freeze-dried and ground with an easy to adapt procedure using standard lab equipment. Grain size of the finely ground samples ranged from fine to coarse silt (2–63 µm), which guarantees homogeneity for representative subsampling, a widespread problem in sediment trap research. Subsamples of the ground material were perfectly suitable for a variety of biogeochemical measurements, and even at very low particle fluxes we were able to get a detailed insight into various parameters characterizing the sinking particles. The methods and recommendations described here are a key improvement for sediment trap applications in mesocosms, as they facilitate the processing of large amounts of samples and allow for high-quality biogeochemical flux data.

Description: Ocean acidification is challenging phenotypic plasticity of individuals and populations. Calanoid copepods (zooplankton) are shown to be fairly plastic against altered pH conditions, and laboratory studies indicate that transgenerational effects are one mechanism behind this plasticity. We studied phenotypic plasticity of the copepod Acartia sp. in the course of a pelagic, large-volume mesocosm study that was conducted to investigate ecosystem and biogeochemical responses to ocean acidification. We measured copepod egg production rate, egg-hatching success, adult female size and adult female antioxidant capacity (ORAC) as a function of acidification (fCO2  ∼  365–1231 µatm) and as a function of quantity and quality of their diet. We used an egg transplant experiment to reveal whether transgenerational effects can alleviate the possible negative effects of ocean acidification on offspring development. We found significant negative effects of ocean acidification on adult female size. In addition, we found signs of a possible threshold at high fCO2, above which adaptive maternal effects cannot alleviate the negative effects of acidification on egg-hatching and nauplii development. We did not find support for the hypothesis that insufficient food quantity (total particulate carbon 〈 55 µm) or quality (C : N) weakens the transgenerational effects. However, females with high-ORAC-produced eggs with high hatching success. Overall, these results indicate that Acartia sp. could be affected by projected near-future CO2 levels

Description: Anthropogenic carbon dioxide (CO2) emissions are reducing the pH in the world's oceans. The plankton community is a key component driving biogeochemical fluxes, and the effect of increased CO2 on plankton is critical for understanding the ramifications of ocean acidification on global carbon fluxes. We determined the plankton community composition and measured primary production, respiration rates and carbon export (defined here as carbon sinking out of a shallow, coastal area) during an ocean acidification experiment. Mesocosms ( ∼  55 m3) were set up in the Baltic Sea with a gradient of CO2 levels initially ranging from ambient ( ∼  240 µatm), used as control, to high CO2 (up to  ∼  1330 µatm). The phytoplankton community was dominated by dinoflagellates, diatoms, cyanobacteria and chlorophytes, and the zooplankton community by protozoans, heterotrophic dinoflagellates and cladocerans. The plankton community composition was relatively homogenous between treatments. Community respiration rates were lower at high CO2 levels. The carbon-normalized respiration was approximately 40 % lower in the high-CO2 environment compared with the controls during the latter phase of the experiment. We did not, however, detect any effect of increased CO2 on primary production. This could be due to measurement uncertainty, as the measured total particular carbon (TPC) and combined results presented in this special issue suggest that the reduced respiration rate translated into higher net carbon fixation. The percent carbon derived from microscopy counts (both phyto- and zooplankton), of the measured total particular carbon (TPC), decreased from  ∼  26 % at t0 to  ∼  8 % at t31, probably driven by a shift towards smaller plankton (〈 4 µm) not enumerated by microscopy. Our results suggest that reduced respiration leads to increased net carbon fixation at high CO2. However, the increased primary production did not translate into increased carbon export, and consequently did not work as a negative feedback mechanism for increasing atmospheric CO2 concentration.

Description: Studies investigating the effect of increasing CO2 levels on the phosphorus cycle in natural waters are lacking although phosphorus often controls phytoplankton development in aquatic systems. The aim of our study was to analyze effects of elevated CO2 levels on phosphorus pool sizes and uptake. Therefore, we conducted a CO2-manipulation mesocosm experiment in the Storfjärden (western Gulf of Finland, Baltic Sea) in summer 2012. We compared the phosphorus dynamics in different mesocosm treatments but also studied them outside the mesocosms in the surrounding fjord water. In the mesocosms as well as in surface waters of Storfjärden, dissolved organic phosphorus (DOP) concentrations of 0.26 ± 0.03 and 0.23 ± 0.04 μmol L−1, respectively, formed the main fraction of the total P-pool (TP), whereas phosphate (PO4) constituted the lowest fraction with mean concentration of 0.15 ± 0.02 μmol L−1 and 0.17 ± 0.07 μmol L−1 in the mesocosms and in the fjord, respectively. Uptake of PO4 ranged between 0.6 and 3.9 nmol L−1 h−1 of which ~ 86 % (mesocosms) and ~ 72 % (fjord) were realized by the size fraction 〈 3 μm. Adenosine triphosphate (ATP) uptake revealed that additional P was supplied from organic compounds accounting for 25–27 % of P provided by PO4 only. CO2 additions did not cause significant changes in phosphorus (P) pool sizes, DOP composition, and uptake of PO4 and ATP when the whole study period was taken into account. About 18 % of PO4 was transformed into POP, whereby the major proportion (~ 82 %) was converted into DOP suggesting that the conversion of PO4 to DOP is the main pathway of the PO4 turnover. We observed that significant relationships (e.g., between POP and Chl a) in the untreated mesocosms vanished under increased fCO2 conditions. Consequently, it can be hypothesized that the relationship between POP formation and phytoplankton growth changed under elevated CO2 conditions. Significant short-term effects were observed for PO4 and particulate organic phosphorus (POP) pool sizes in CO2 treatments 〉 1000 μatm during periods when phytoplankton started to grow.

Description: O2 minimum zones (OMZ) of the world's oceans are important locations for microbial dissimilatory NO3- reduction and subsequent loss of combined nitrogen (N) to biogenic N2 gas. This is particularly so when the OMZ is coupled to a region of high productivity leading to high rates of N-loss as found in the coastal upwelling region off Peru. Stable N isotope ratios (and O in the case of NO3- and NO2-) can be used as natural tracers of OMZ N-cycling because of distinct kinetic isotope effects associated with microbially-mediated N-cycle transformations. Here we present NO2- and NO3- stable isotope data from the nearshore upwelling region off Callao, Peru. Subsurface O2 was generally depleted below about 30 m depth with O2 less than 10 μM, while NO2- concentrations were high, ranging from 6 to 10 μM and NO3- was in places strongly depleted to near 0 μM. We observed for the first time, a positive linear relationship between NO2- δ15N and δ18O at our coastal stations, analogous to that of NO3- N and O isotopes during assimilatory and dissimilatory reduction. This relationship is likely the result of rapid NO2- turnover due to higher organic matter flux in these coastal upwelling waters. No such relationship was observed at offshore stations where slower turnover of NO2- facilitates dominance of isotope exchange with water. We also evaluate the overall isotope fractionation effect for N-loss in this system using several approaches that vary in their underlying assumptions. While there are differences in apparent fractionation factor (ε) for N-loss as calculated from the δ15N of [NO3-], DIN, or biogenic N2, values for ε are generally much lower than previously reported, reaching as low as 6.5‰. A possible explanation is the influence of sedimentary N-loss at our inshore stations which incurs highly suppressed isotope fractionation.

Description: Increasing atmospheric carbon dioxide (CO2) is changing seawater chemistry towards reduced pH, which consequently affects various properties of marine organisms. Coastal and brackish water communities are expected to be less affected by ocean acidification (OA) as these communities are typically adapted to high fluctuations in CO2 and pH. Here we investigate the response of a coastal brackish water plankton community to increasing CO2 levels as projected for the coming decades and the end of this century in terms of community and biochemical fatty acid (FA) composition. A Baltic Sea plankton community was enclosed in a set of off-shore mesocosms and subjected to a CO2 gradient ranging from natural concentrations (~347 μatm pCO2) up to values projected for the year 2100 (~1333 μatm pCO2). We show that the phytoplankton community composition was resilient to CO2 and did not diverge between the treatments. Seston FA composition was influenced by community composition, which in turn was driven by silicate and phosphate limitation in the mesocosms, and showed no difference between the CO2 treatments. These results suggest that CO2 effects are dampened in coastal communities that already experience high natural fluctuations in pCO2. Although this coastal plankton community was tolerant to high pCO2 levels, hypoxia and CO2 uptake by the sea can aggravate acidification and may lead to pH changes outside the currently experienced range for coastal organisms.

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.