ALBERT

Description: Oxygen minimum zones (OMZs) are often characterized by nitrogen-to-phosphorus (N:P) ratios far lower than the canonical Redfield ratio. Whereas, the importance of variable stoichiometry in phytoplankton has long been recognized, variations in zooplankton stoichiometry have received much less attention. Here we combine observations from two shipboard mesocosm nutrient enrichment experiments with an optimality-based plankton ecosystem model, designed to elucidate the roles of different trophic levels and elemental stoichiometry. Pre-calibrated microzooplankton parameter sets represent foraging strategies of dinoflagellates and ciliates in our model. Our results suggest that remineralization is largely driven by omnivorous ciliates and dinoflagellates, and highlight the importance of intraguild predation. We hypothesize that microzooplankton respond to changes in food quality in terms of nitrogen-to-carbon (N:C) ratios, rather than nitrogen-to-phosphorus (N:P) ratios, by allowing variations in their phosphorus-to-carbon (P:C) ratio. Our results point toward an important biogeochemical role of flexible microzooplankton stoichiometry

Description: The sediment-water interface is an important site for material exchange in marine systems and harbor unique microbial habitats. The flux of nutrients, metals, and greenhouse gases at this interface may be severely dampened by the activity of microorganisms and abiotic redox processes, leading to the “benthic filter” concept. In this study, we investigate the spatial variability, mechanisms and quantitative importance of a microbially-dominated benthic filter for dissolved sulfide in the Eastern Gotland Basin (Baltic Sea) that is located along a dynamic redox gradient between 65 and 173 m water depth. In August-September 2013, high resolution (0.25 mm minimum) vertical microprofiles of redox-sensitive species were measured in surface sediments with solid-state gold-amalgam voltammetric microelectrodes. The highest sulfide consumption (2.73–3.38 mmol m−2 day−1) occurred within the top 5 mm in sediments beneath a pelagic hypoxic transition zone (HTZ, 80–120 m water depth) covered by conspicuous white bacterial mats of genus Beggiatoa. A distinct voltammetric signal for polysulfides, a transient sulfur oxidation intermediate, was consistently observed within the mats. In sediments under anoxic waters (〉140 m depth), signals for Fe(II) and aqueous FeS appeared below a subsurface maximum in dissolved sulfide, indicating a Fe(II) flux originating from older sediments presumably deposited during the freshwater Ancylus Lake that preceded the modern Baltic Sea. Our results point to a dynamic benthic sulfur cycling in Gotland Basin where benthic sulfide accumulation is moderated by microbial sulfide oxidation at the sediment surface and FeS precipitation in deeper sediment layers. Upscaling our fluxes to the Baltic Proper; we find that up to 70% of the sulfide flux (2281 kton yr−1) toward the sediment-seawater interface in the entire basin can be consumed at the microbial mats under the HTZ (80–120 m water depth) while only about 30% the sulfide flux effuses to the bottom waters (〉120 m depth). This newly described benthic filter for the Gotland Basin must play a major role in limiting the accumulation of sulfide in and around the deep basins of the Baltic Sea.

Description: Nitrous oxide (N2O) is a powerful greenhouse gas principally produced by nitrification and denitrification in the marine environment. Observations were made in the eastern South Pacific (ESP), between 10° and 60°S, and ~75°–88°W, from intermediate waters targeting Antarctic Intermediate Water (AAIW) at potential density of 27.0–27.1 kg m−3. Between 60° and 20°S, a gradual equatorward increase of N2O from 8 to 26 nmol L−1 was observed at density 27.0–27.1 kg m−3 where AAIW penetrates. Positive correlations were found between apparent N2O production (ΔN2O) and O2 utilization (AOU), and between ΔN2O and NO−3, which suggested that local N2O production is predominantly produced by nitrification. Closer to the equator, between 20° and 10°S at AAIW core, a strong N2O increase up to 75 nmol L−1 was observed. Because negative correlations were found between ΔN2O vs. NO−3 and ΔN2O vs. N* (a Nitrogen deficit index) and because ΔN2O and AOU do not follow a linear trend, we suspect that, in addition to nitrification, denitrification also takes place in N2O cycling. By making use of water mass mixing analyses, we show that an increase in N2O occurs in the region where high oxygen from AAIW merges with low oxygen from Equatorial Subsurface Water (ESSW), creating favorable conditions for local N2O production. We conclude that the non-linearity in the relationship between N2O and O2 is a result of mixing between two water masses with very different source characteristics, paired with the different time frames of nitrification and denitrification processes that impact water masses en route before they finally meet and mix in the ESP region.

Description: The microbial community response to petroleum seepage was investigated in a whole round sediment core (16 cm length) collected nearby natural hydrocarbon seepage structures in the Caspian Sea, using a newly developed Sediment-Oil-Flow-Through (SOFT) system. Distinct redox zones established and migrated vertically in the core during the 190 days-long simulated petroleum seepage. Methanogenic petroleum degradation was indicated by an increase in methane concentration from 8 μM in an untreated core compared to 2300 μM in the lower sulfate-free zone of the SOFT core at the end of the experiment, accompanied by a respective decrease in the δ13C signal of methane from -33.7 to -49.5‰. The involvement of methanogens in petroleum degradation was further confirmed by methane production in enrichment cultures from SOFT sediment after the addition of hexadecane, methylnapthalene, toluene, and ethylbenzene. Petroleum degradation coupled to sulfate reduction was indicated by the increase of integrated sulfate reduction rates from 2.8 SO42-m-2 day-1 in untreated cores to 5.7 mmol SO42-m-2 day-1 in the SOFT core at the end of the experiment, accompanied by a respective accumulation of sulfide from 30 to 447 μM. Volatile hydrocarbons (C2–C6 n-alkanes) passed through the methanogenic zone mostly unchanged and were depleted within the sulfate-reducing zone. The amount of heavier n-alkanes (C10–C38) decreased step-wise toward the top of the sediment core and a preferential degradation of shorter (〈C14) and longer chain n-alkanes (〉C30) was seen during the seepage. This study illustrates, to the best of our knowledge, for the first time the development of methanogenic petroleum degradation and the succession of benthic microbial processes during petroleum passage in a whole round sediment core.

Description: Biodiversity and conservation data are generally costly to collect, particularly in the marine realm. Hence, data collected for a given—often scientific—purpose are occasionally contributed toward secondary needs, such as policy implementation or other types of decision-making. However, while the quality and accessibility of marine biodiversity and conservation data have improved over the past decade, the ways in which these data can be used to develop and implement relevant management and conservation measures and actions are not always explicit. For this reason, there are a number of scientifically-sound datasets that are not used systematically to inform policy and decisions. Transforming these marine biodiversity and conservation datasets into knowledge products that convey the information required by policy- and decision-makers is an important step in strengthening knowledge exchange across the science-policy interface. Here, we identify seven characteristics of a selection of online biodiversity and conservation knowledge products that contribute to their ability to support policy- and decision-making in the marine realm (as measured by e.g., mentions in policy resolutions/decisions, or use for reporting under selected policy instruments; use in high-level screening for areas of biodiversity importance). These characteristics include: a clear policy mandate; established networks of collaborators; iterative co-design of a user-friendly interface; standardized, comprehensive and documented methods with quality assurance; consistent capacity and succession planning; accessible data and value-added products that are fit-for-purpose; and metrics of use collated and reported. The outcomes of this review are intended to: (a) support data creators/owners/providers in designing and curating biodiversity and conservation knowledge products that have greater influence, and hence impact, in policy- and decision-making, and (b) provide recommendations for how decision- and policy-makers can support the development, implementation, and sustainability of robust biodiversity and conservation knowledge products through the framing of marine policy and decision-making frameworks.

Description: Cold-water coral ecosystems are considered hot-spots of biodiversity and biomass production and may be a regionally important contributor to carbonate production. The impact of these ecosystems on biogeochemical processes and carbonate preservation in associated sediments were studied at Røst Reef and Traenadjupet Reef, two modern (post-glacial) cold-water coral reefs on the Mid-Norwegian shelf. Sulfate and iron reduction as well as carbonate dissolution and precipitation were investigated by combining pore-water geochemical profiles, steady state modeling, as well as solid phase analyses and sulfate reduction rate measurements on gravity cores of up to 3.25 m length. Low extents of sulfate depletion and dissolved inorganic carbon (DIC) production, combined with sulfate reduction rates not exceeding 3 nmol S cm−3 d−1, suggested that overall anaerobic carbon mineralization in the sediments was low. These data showed that the coral fragment-bearing siliciclastic sediments were effectively decoupled from the productive pelagic ecosystem by the complex reef surface framework. Organic matter being mineralized by sulfate reduction was calculated to consist of 57% carbon bound in CH2O groups and 43% carbon in -CH2- groups. Methane concentrations were below 1 μM, and failed to support the hypothesis of a linkage between the distribution of cold-water coral reefs and the presence of hydrocarbon seepage. Reductive iron oxide dissolution linked to microbial sulfate reduction buffered the pore-water carbonate system and inhibited acid-driven coral skeleton dissolution. A large pool of reactive iron was available leading to the formation of iron sulfide minerals. Constant pore-water Ca2+, Mg2+ and Sr2+ concentrations in most cores and decreasing Ca2+ and Sr2+ concentrations with depth in core 23–18 GC indicated diagenetic carbonate precipitation. This was consistent with the excellent preservation of buried coral fragments.

Description: In order to test the influences of ocean acidification on the ocean pelagic ecosystem, so far the largest CO2 manipulation mesocosm study (European Project on Ocean Acidification, EPOCA) was performed in Kings Bay (Kongsfjorden), Spitsbergen. During a 30 day incubation, bacterial diversity was investigated using DNA fingerprinting and clone library analysis of bacterioplankton samples. Terminal restriction fragment length polymorphism (T-RFLP) analysis of the PCR amplicons of the 16S rRNA genes revealed that general bacterial diversity, taxonomic richness and community structure were influenced by the variation of productivity during the time of incubation, but not the degree of ocean acidification. A BIOENV analysis suggested a complex control of bacterial community structure by various biological and chemical environmental parameters. The maximum apparent diversity of bacterioplankton (i.e., the number of T-RFs) in high and low pCO2 treatments differed significantly. A negative relationship between the relative abundance of Bacteroidetes and pCO2 levels was observed for samples at the end of the experiment by the combination of T-RFLP and clone library analysis. Our study suggests that ocean acidification affects the development of bacterial assemblages and potentially impacts the ecological function of the bacterioplankton in the marine ecosystem.

Description: One of the major challenges in ecological stoichiometry is to establish how environmental changes in resource availability may affect both the biochemical composition of organisms and the species composition of communities. This is a pressing issue in many coastal waters, where anthropogenic activities have caused large changes in riverine nutrient inputs. Here we investigate variation in the biochemical composition and synthesis of amino acids, fatty acids (FA), and carbohydrates in mixed phytoplankton communities sampled from the North Sea. The communities were cultured in chemostats supplied with different concentrations of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) to establish four different types of resource limitations. Diatoms dominated under N-limited, N+P limited and P-limited conditions. Cyanobacteria became dominant in one of the N-limited chemostats and green algae dominated in the one P-limited chemostat and under light-limited conditions. Changes in nutrient availability directly affected amino acid content, which was lowest under N and N+P limitation, higher under P-limitation and highest when light was the limiting factor. Storage carbohydrate content showed the opposite trend and storage FA content seemed to be co-dependent on community composition. The synthesis of essential amino acids was affected under N and N+P limitation, as the transformation from non-essential to essential amino acids decreased at DIN:DIP ≤ 6. The simple community structure and clearly identifiable nutrient limitations confirm and clarify previous field findings in the North Sea. Our results show that different phytoplankton groups are capable of adapting their key biosynthetic rates and hence their biochemical composition to different degrees when experiencing shifts in nutrient availability. This will have implications for phytoplankton growth, community structure, and the nutritional quality of phytoplankton as food for higher trophic levels.

Description: The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR). Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS). Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Description: The Atlantic meridional overturning circulation (AMOC) carries large amounts of heat into the North Atlantic influencing climate regionally as well as globally. Palaeo-records and simulations with comprehensive climate models suggest that the positive salt-advection feedback may yield a threshold behaviour of the system. That is to say that beyond a certain amount of freshwater flux into the North Atlantic, no meridional overturning circulation can be sustained. Concepts of monitoring the AMOC and identifying its vicinity to the threshold rely on the fact that the volume flux defining the AMOC will be reduced when approaching the threshold. Here we advance conceptual models that have been used in a paradigmatic way to understand the AMOC, by introducing a density-dependent parameterization for the Southern Ocean eddies. This additional degree of freedom uncovers a mechanism by which the AMOC can increase with additional freshwater flux into the North Atlantic, before it reaches the threshold and collapses: an AMOC that is mainly wind-driven will have a constant upwelling as long as the Southern Ocean winds do not change significantly. The downward transport of tracers occurs either in the northern sinking regions or through Southern Ocean eddies. If freshwater is transported, either atmospherically or via horizontal gyres, from the low to high latitudes, this would reduce the eddy transport and by continuity increase the northern sinking which defines the AMOC until a threshold is reached at which the AMOC cannot be sustained. If dominant in the real ocean this mechanism would have significant consequences for monitoring the AMOC.

Description: We present bathymetry and hydrological observations collected in the summer of 2014 from two fjord systems in southeastern Greenland with a multibeam sonar system. Our results provide a detailed bathymetric map of the fjord complex around the island of Skjoldungen in Skjoldungen Fjord and the outer part of Timmiarmiut Fjord and show far greater depths compared to the International Bathymetric Chart of the Arctic Ocean. The hydrography collected shows different properties in the fjords with the bottom water masses below 240 m in Timmiarmiut Fjord being 1–2 °C warmer than in the two fjords around Skjoldungen, but data also illustrate the influence of sills on the exchange of deeper water masses within fjords. Moreover, evidence of subglacial discharge in Timmiarmiut Fjord, which is consistent with satellite observations of ice mélange set into motion, adds to our increasing understanding of the distribution of subglacial meltwater.

Description: Ocean acidification resulting from the uptake of anthropogenic carbon dioxide (CO2) by the ocean is considered a major threat to marine ecosystems. Here we examined the effects of ocean acidification on microbial community dynamics in the eastern Baltic Sea during the summer of 2012 when inorganic nitrogen and phosphorus were strongly depleted. Large-volume in situ mesocosms were employed to mimic present, future and far future CO2 scenarios. All six groups of phytoplankton enumerated by flow cytometry ( 〈  20 µm cell diameter) showed distinct trends in net growth and abundance with CO2 enrichment. The picoeukaryotic phytoplankton groups Pico-I and Pico-II displayed enhanced abundances, whilst Pico-III, Synechococcus and the nanoeukaryotic phytoplankton groups were negatively affected by elevated fugacity of CO2 (fCO2). Specifically, the numerically dominant eukaryote, Pico-I, demonstrated increases in gross growth rate with increasing fCO2 sufficient to double its abundance. The dynamics of the prokaryote community closely followed trends in total algal biomass despite differential effects of fCO2 on algal groups. Similarly, viral abundances corresponded to prokaryotic host population dynamics. Viral lysis and grazing were both important in controlling microbial abundances. Overall our results point to a shift, with increasing fCO2, towards a more regenerative system with production dominated by small picoeukaryotic phytoplankton.

Description: In order to identify the biogeochemical parameters controlling pCO2, total chlorophyll a, and dimethyl sulfide (DMS) concentrations during the North East Atlantic Spring Bloom (NASB), we used previously unpublished particulate and dissolved elemental concentrations to construct several linear regression models; first by hypothesis-testing, and then with exhaustive stepwise linear regression followed by leave-one-out cross-validation. The field data was obtained along a latitudinal transect from the Azores Islands to the North Atlantic, and best-fit models (determined by lowest predictive error) of up to three variables are presented. Total chlorophyll a is predicted best by biomass (POC, PON) parameters and by pigments characteristic of picophytoplankton for the southern section of the sampling transect (from the Azores to the Rockhall-Hatton Plateau) and coccolithophores in the northern portion (from the Rockhall-Hatton Plateau to the Denmark Strait). Both the pCO2 and DMS models included variables traditionally associated with the development of the NASB such as mixed-layer depth and with Fe, Si, and P-deplete conditions (dissolved Fe, dissolved and biogenic silica, dissolved PO3−4). However, the regressions for pCO2 and DMS also include intracellular V and Mo concentrations, respectively. Mo is involved in DMS production as a cofactor in dimethylsulfoxide reductase. No significant biological role for V has yet been determined, although intracellular V is significantly correlated (p-value 〈0.05) with biogenic silica (R2 = 0.72) and total chlorophyll a (R2 = 0.49) while the same is not true for its biogeochemical analogue Mo, suggesting active uptake of V by phytoplankton. Our statistical analysis suggests these two lesser-studied metals may play more important roles in bloom dynamics than previously thought, and highlights a need for studies focused on determining their potential biological requirements and cell quotas.

Description: Pliensbachian and Toarcian Ostracoda first described by Exton (Geological Paper, Carleton University, Ottawa, 79: 1–104 1979) from the Lusitanian Basin, west-central Portugal have been re-examined. As a result, a greater diversity in the Ostracoda (80 species) is now recognized. Two species are newly described (Eucytherura zambujalensis sp. nov., Ektyphocythere mediodepressa sp. nov.) from the marls and calcareous shales of the Maria Pares Hill section near the village of Zambujal. Poor preservation precludes a complete taxonomic review of the present material. Five ostracod zones are proposed; Gammacythere ubiquita–Ogmoconchella gruendeli Zone, Poly cope cerasia–Polycope cincinnata Zone, Liasina lanceolata–Ogmoconcha convexa Zone, Bairdiacypris rectangularis–Kinkelinella sermoisensis Zone, and Cytherella toarcensis-Kinkelinella costata Zone. Although the ostracod assemblages possess strong similarities to those described from Northwest Europe, some of the Zambujal assemblages are dominated by the genus Polycope. A marked faunal turnover, in association with the extinction of the Metacopina occurs in the lower Subzone of the tenuicostatum Zone of Lower Toarcian age. These faunal events are discussed in relation to changing environmental conditions.

Description: Biogeochemical models, capturing the major feedbacks of the pelagic ecosystem of the world ocean, are today often embedded into Earth system models which are increasingly used for decision making regarding climate policies. These models contain poorly constrained parameters (e.g., maximum phytoplankton growth rate), which are typically adjusted until the model shows reasonable behavior. Systematic approaches determine these parameters by minimizing the misfit between the model and observational data. In most common model approaches, however, the underlying functions mimicking the biogeochemical processes are nonlinear and non-convex. Thus, systematic optimization algorithms are likely to get trapped in local minima and might lead to non-optimal results. To judge the quality of an obtained parameter estimate, we propose determining a preferably large lower bound for the global optimum that is relatively easy to obtain and that will help to assess the quality of an optimum, generated by an optimization algorithm. Due to the unavoidable noise component in all observations, such a lower bound is typically larger than zero. We suggest deriving such lower bounds based on typical properties of biogeochemical models (e.g., a limited number of extremes and a bounded time derivative). We illustrate the applicability of the method with two real-world examples. The first example uses real-world observations of the Baltic Sea in a box model setup. The second example considers a three-dimensional coupled ocean circulation model in combination with satellite chlorophyll a.

Description: The late stage of the North East Atlantic (NEA) spring bloom was investigated during June 2005 along a transect section from 45 to 66° N between 15 and 20° W in order to characterize the contribution of siliceous and calcareous phytoplankton groups and describe their distribution in relation to environmental factors. We measured several biogeochemical parameters such as nutrients, surface trace metals, algal pigments, biogenic silica (BSi), particulate inorganic carbon (PIC) or calcium carbonate, particulate organic carbon, nitrogen and phosphorus (POC, PON and POP, respectively), as well as transparent exopolymer particles (TEP). Results were compared with other studies undertaken in this area since the JGOFS NABE program. Characteristics of the spring bloom generally agreed well with the accepted scenario for the development of the autotrophic community. The NEA seasonal diatom bloom was in the late stages when we sampled the area and diatoms were constrained to the northern part of our transect, over the Icelandic Basin (IB) and Icelandic Shelf (IS). Coccolithophores dominated the phytoplankton community, with a large distribution over the Rockall-Hatton Plateau (RHP) and IB. The Porcupine Abyssal Plain (PAP) region at the southern end of our transect was the region with the lowest biomass, as demonstrated by very low Chla concentrations and a community dominated by picophytoplankton. Early depletion of dissolved silicic acid (DSi) and increased stratification of the surface layer most likely triggered the end of the diatom bloom, leading to coccolithophore dominance. The chronic Si deficiency observed in the NEA could be linked to moderate Fe limitation, which increases the efficiency of the Si pump. TEP closely mirrored the distribution of both biogenic silica at depth and prymnesiophytes in the surface layer suggesting the sedimentation of the diatom bloom in the form of aggregates, but the relative contribution of diatoms and coccolithophores to carbon export in this area still needs to be resolved.

Description: Very short-lived substances (VSLS) contribute as source gases significantly to the tropospheric and stratospheric bromine loading. At present, an estimated 25% of stratospheric bromine is of oceanic origin. In this study, we investigate how climate change may impact the ocean- atmosphere flux of brominated VSLS, their atmospheric transport, and chemical transformations and evaluate how these changes will affect stratospheric ozone over the 21st century. Under the assumption of fixed ocean water concentrations and RCP6.0 scenario, we find an increase of the ocean- atmosphere flux of brominated VSLS of about 8-10% by the end of the 21st century compared to present day. A decrease in the tropospheric mixing ratios of VSLS and an increase in the lower stratosphere are attributed to changes in atmospheric chemistry and transport. Our model simulations reveal that this increase is counteracted by a corresponding reduction of inorganic bromine. Therefore the total amount of bromine from VSLS in the stratosphere will not be changed by an increase in upwelling. Part of the increase of VSLS in the tropical lower stratosphere results from an increase in the corresponding tropopause height. As the depletion of stratospheric ozone due to bromine depends also on the availability of chlorine, we find the impact of bromine on stratospheric ozone at the end of the 21st century reduced compared to present day. Thus, these studies highlight the different factors influencing the role of brominated VSLS in a future climate

Description: Reanalysis data sets are widely used to understand atmospheric processes and past variability, and are often used to stand in as "observations" for comparisons with climate model output. Because of the central role of water vapor (WV) and ozone (O3) in climate change, it is important to understand how accurately and consistently these species are represented in existing global reanalyses. In this paper, we present the results of WV and O3 intercomparisons that have been performed as part of the SPARC (Stratosphere–troposphere Processes and their Role in Climate) Reanalysis Intercomparison Project (S-RIP). The comparisons cover a range of timescales and evaluate both inter-reanalysis and observation-reanalysis differences. We also provide a systematic documentation of the treatment of WV and O3 in current reanalyses to aid future research and guide the interpretation of differences amongst reanalysis fields. The assimilation of total column ozone (TCO) observations in newer reanalyses results in realistic representations of TCO in reanalyses except when data coverage is lacking, such as during polar night. The vertical distribution of ozone is also relatively well represented in the stratosphere in reanalyses, particularly given the relatively weak constraints on ozone vertical structure provided by most assimilated observations and the simplistic representations of ozone photochemical processes in most of the reanalysis forecast models. However, significant biases in the vertical distribution of ozone are found in the upper troposphere and lower stratosphere in all reanalyses. In contrast to O3, reanalysis estimates of stratospheric WV are not directly constrained by assimilated data. Observations of atmospheric humidity are typically used only in the troposphere, below a specified vertical level at or near the tropopause. The fidelity of reanalysis stratospheric WV products is therefore mainly dependent on the reanalyses' representation of the physical drivers that influence stratospheric WV, such as temperatures in the tropical tropopause layer, methane oxidation, and the stratospheric overturning circulation. The lack of assimilated observations and known deficiencies in the representation of stratospheric transport in reanalyses result in much poorer agreement amongst observational and reanalysis estimates of stratospheric WV. Hence, stratospheric WV products from the current generation of reanalyses should generally not be used in scientific studies.

Description: The Sumatran subduction zone exhibits strong seismic and tsunamogenic potential with the prominent examples of the 2004, 2005 and 2007 earthquakes. Here, we invert travel time data of local earthquakes for vp and vp/vs velocity models of the central Sumatran forearc. Data were acquired by an amphibious seismometer network consisting of 52 land stations and 10 ocean bottom seismometers located on a segment of the Sumatran subduction zone that had not ruptured in a great earthquake since 1797 but witnessed recent ruptures to the north in 2005 (Nias earthquake, Mw = 8.7) and to the south in 2007 (Bengkulu earthquake, Mw = 8.5). 2D and 3D vp velocity anomalies reveal the downgoing slab and the sedimentary basins. Although the seismicity pattern in the study area appears to be strongly influenced by the obliquely subducting Investigator Fracture Zone to at least 200 km depth, the 3D velocity model shows prevailing trench parallel structures at depths of the plate interface. The tomographic model suggests a thinned crust below the basin east of the forearc islands (Nias, Pulau Batu, Siberut) at ~ 180 km distance to the trench. Vp velocities beneath the magmatic arc and the Sumatran fault zone SFZ are around 5 km/s at 10 km depth and the vp/vs ratios in the uppermost 10 km are low, indicating the presence of felsic lithologies typical for continental crust. We find moderately elevated vp/vs values of 1.85 at ~ 150 km distance to the trench in the region of the Mentawai fault. Vp/vs ratios suggest absence of large scale alteration of the mantle wedge and might explain why the seismogenic plate interface (observed as a locked zone from geodetic data) extends below the continental forearc Moho in Sumatra. Reduced vp velocities beneath the forearc basin covering the region between Mentawai Islands and the Sumatra mainland possibly reflect a reduced thickness of the overriding crust.

Description: In this study ship- and AUV-based multibeam data from the German Mn-nodule license area in the Clarion-Clipperton Zone (CCZ; eastern Pacific) are linked to ground truth data from optical imaging. Photographs obtained by an AUV enable semi-quantitative assessments of nodule coverage at a spatial resolution in the range of meters. Together with high resolution AUV bathymetry this revealed a correlation of small-scale terrain variations (〈 5 m horizontally, 〈 1 m vertically) with nodule abundance. In the presented data set, increased nodule coverage could be correlated with slopes 〉 1.8° and concave terrain. On a more regional scale, factors such as the geological setting (existence of horst and graben structures, sediment thickness, outcropping basement) and influence of bottom currents seem to play an essential role for the spatial variation of nodule abundance and the related hard substrate habitat. AUV imagery was also successfully employed to map the distribution of re-settled sediment following a disturbance and sediment cloud generation during a sampling deployment of an Epibenthic Sledge. Data from before and after the "disturbance" allows a direct assessment of the impact. Automated image processing analyzed the nodule coverage at the seafloor, revealing nodule blanketing by resettling of suspended sediment within 16 hours after the disturbance. The visually detectable impact was spatially limited to a maximum of 100m distance from the disturbance track, downstream of the bottom water current. A correlation with high resolution AUV bathymetry reveals that the blanketing pattern varies in extent by tens of meters, strictly following the bathymetry, even in areas of only slightly undulating seafloor (〈 1 m vertical change). These results highlight the importance of detailed terrain knowledge when engaging in resource assessment studies for nodule abundance estimates and defining minable areas. At the same time, it shows the importance of high resolution mapping for detailed benthic habitat studies that show a heterogeneity at scales of 10 m to 100 m. Terrain knowledge is also needed to determine the scale of the impact by seafloor sediment blanketing during mining-operations.

Description: The ocean is a major sink for anthropogenic carbon dioxide (CO2), with the CO2 uptake causing changes to ocean chemistry. To monitor these changes and provide a chemical background for biological and biogeochemical studies, high quality partial pressure of CO2 (pCO2) sensors are required, with suitable accuracy and precision for ocean measurements. Optodes have the potential to measure in situ pCO2 without the need for wet chemicals or bulky gas equilibration chambers that are typically used in pCO2 systems. However, optodes are still in an early developmental stage compared to more established equilibrator-based pCO2 systems. In this study, we performed a laboratory-based characterization of a time-domain dual lifetime referencing pCO2 optode system. The pCO2 optode spot was illuminated with low intensity light (0.2 mA, 0.72 mW) to minimize spot photobleaching. The spot was calibrated using an experimental gas calibration rig prior to deployment, with a determined response time (τ63) of 50 s at 25°C. The pCO2 optode was deployed as an autonomous shipboard underway system across the high latitude North Atlantic Ocean with a resolution of ca.10 measurements per hour. The optode data was validated with a secondary shipboard equilibrator-based infrared pCO2 instrument, and pCO2 calculated from discrete samples of dissolved inorganic carbon and total alkalinity. Further verification of the pCO2 optode data was achieved using complimentary variables such as nutrients and dissolved oxygen. The shipboard precision of the pCO2 sensor was 9.5 μatm determined both from repeat measurements of certified reference materials and from the standard deviation of seawater measurements while on station. Finally, the optode deployment data was used to evaluate the physical and biogeochemical controls on pCO2.

Description: Climate-driven changes in environmental conditions have significant and complex effects on marine ecosystems. Variability in phytoplankton elements and biochemicals can be important for global ocean biogeochemistry and ecological functions, while there is currently limited understanding on how elements and biochemicals respond to the changing environments in key coccolithophore species such as Emiliania huxleyi. We investigated responses of elemental stoichiometry and fatty acids (FAs) in a strain of E. huxleyi under three temperatures (12, 18 and 24 °C), three N : P supply ratios (molar ratios 10:1, 24:1 and 63:1) and two pCO2 levels (560 and 2400 µatm). Overall, C : N : P stoichiometry showed the most pronounced response to N : P supply ratios, with high ratios of particulate organic carbon vs. particulate organic nitrogen (POC : PON) and low ratios of PON vs. particulate organic phosphorus (PON : POP) in low-N media, and high POC : POP and PON : POP in low-P media. The ratio of particulate inorganic carbon vs. POC (PIC : POC) and polyunsaturated fatty acid proportions strongly responded to temperature and pCO2, both being lower under high pCO2 and higher with warming. We observed synergistic interactions between warming and nutrient deficiency (and high pCO2) on elemental cellular contents and docosahexaenoic acid (DHA) proportion in most cases, indicating the enhanced effect of warming under nutrient deficiency (and high pCO2). Our results suggest differential sensitivity of elements and FAs to the changes in temperature, nutrient availability and pCO2 in E. huxleyi, which is to some extent unique compared to non-calcifying algal classes. Thus, simultaneous changes of elements and FAs should be considered when predicting future roles of E. huxleyi in the biotic-mediated connection between biogeochemical cycles, ecological functions and climate change.

Description: The pre-industrial millennium is among the periods selected by the Paleoclimate Model Intercomparison Project (PMIP) for experiments contributing to the sixth phase of the Coupled Model Intercomparison Project (CMIP6) and the fourth phase of the PMIP (PMIP4). The past1000 transient simulations serve to investigate the response to (mainly) natural forcing under background conditions not too different from today, and to discriminate between forced and internally generated variability on interannual to centennial timescales. This paper describes the motivation and the experimental set-ups for the PMIP4-CMIP6 past1000 simulations, and discusses the forcing agents orbital, solar, volcanic, and land use/land cover changes, and variations in greenhouse gas concentrations. The past1000 simulations covering the pre-industrial millennium from 850 Common Era (CE) to 1849 CE have to be complemented by historical simulations (1850 to 2014 CE) following the CMIP6 protocol. The external forcings for the past1000 experiments have been adapted to provide a seamless transition across these time periods. Protocols for the past1000 simulations have been divided into three tiers. A default forcing data set has been defined for the Tier 1 (the CMIP6 past1000) experiment. However, the PMIP community has maintained the flexibility to conduct coordinated sensitivity experiments to explore uncertainty in forcing reconstructions as well as parameter uncertainty in dedicated Tier 2 simulations. Additional experiments (Tier 3) are defined to foster collaborative model experiments focusing on the early instrumental period and to extend the temporal range and the scope of the simulations. This paper outlines current and future research foci and common analyses for collaborative work between the PMIP and the observational communities (reconstructions, instrumental data).

Description: Although mesoscale ocean eddies are ubiquitous in the Southern Ocean, their average regional and seasonal association with phytoplankton has not been quantified systematically yet. To this end, we identify over 100000 mesoscale eddies with diameters of 50km and more in the Southern Ocean and determine the associated phytoplankton biomass anomalies using satellite-based chlorophyll-a (Chl) as a proxy. The mean Chl anomalies, δChl, associated with these eddies, comprising the upper echelon of the oceanic mesoscale, exceed ±10% over wide regions. The structure of these anomalies is largely zonal, with cyclonic, thermocline lifted, eddies having positive anomalies in the subtropical waters north of the Antarctic Circumpolar Current (ACC) and negative anomalies along its main flow path. The pattern is similar, but reversed for anticyclonic, thermocline deepened eddies. The seasonality of δChl is weak in subtropical waters, but pronounced along the ACC, featuring a seasonal sign switch. The spatial structure and seasonality of the mesoscale δChl can be explained largely by lateral advection, especially local eddy-stirring. A prominent exception is the ACC region in winter, where δChl is consistent with a modulation of phytoplankton light exposure caused by an eddy-induced modification of the mixed layer depth. The clear impact of mesoscale eddies on phytoplankton may implicate a downstream effect on Southern Ocean biogeochemical properties, such as mode water nutrient contents.

Description: The potential harvest of polymetallic nodules will heavily impact the abyssal, soft sediment ecosystem by removing sediment, hard substrate, and associated fauna inside mined areas. It is therefore important to know whether the ecosystem can recover from this disturbance and if so at which rate. The first objective of this study was to measure recovery of phytodetritus processing by the benthic food web from a sediment disturbance experiment in 1989. The second objective was to determine the role of holothurians in the uptake of fresh phytodetritus by the benthic food web. To meet both objectives, large benthic incubation chambers (CUBEs; 50 × 50 × 50 cm) were deployed inside plow tracks (with and without holothurian presence) and at a reference site (holothurian presence, only) at 4100 m water depth. Shortly after deployment, 13C- and 15N-labeled phytodetritus was injected in the incubation chambers and during the subsequent 3-day incubation period, water samples were taken five times to measure the production of 13C-dissolved inorganic carbon over time. At the end of the incubation, holothurians and sediment samples were taken to determine biomass, densities and incorporation of 13C and 15N into bacteria, nematodes, macrofauna, and holothurians. For the first objective, the results showed that biomass of bacteria, nematodes and macrofauna did not differ between reference sites and plow track sites when holothurians were present. Additionally, meiofauna and macrofauna taxonomic composition was not significantly different between the sites. In contrast, total 13C uptake by bacteria, nematodes and holothurians was significantly lower at plow track sites compared to reference sites, though the number of replicates was low. This result suggests that important ecosystem functions such as organic matter processing have not fully recovered from the disturbance that occurred 26 years prior to our study. For the second objective, the analysis indicated that holothurians incorporated 2.16 × 10−3 mmol labile phytodetritus C m−2 d−1 into their biomass, which is one order of magnitude less as compared to bacteria, but 1.3 times higher than macrofauna and one order of magnitude higher than nematodes. Additionally, holothurians incorporated more phytodetritus carbon per unit biomass than macrofauna and meiofauna, suggesting a size-dependence in phytodetritus carbon uptake.

Description: Recently, measurements of oxygen concentration in the ocean-one of the most classical parameters in chemical oceanography-are experiencing a revival. This is not surprising, given the key role of oxygen for assessing the status of the marine carbon cycle and feeling the pulse of the biological pump. The revival, however, has to a large extent been driven by the availability of robust optical oxygen sensors and their painstakingly thorough characterization. For autonomous observations, oxygen optodes are the sensors of choice: They are used abundantly on Biogeochemical-Argo floats, gliders and other autonomous oceanographic observation platforms. Still, data quality and accuracy are often suboptimal, in some part because sensor and data treatment are not always straightforward and/or sensor characteristics are not adequately taken into account. Here, we want to summarize the current knowledge about oxygen optodes, their working principle as well as their behavior with respect to oxygen, temperature, hydrostatic pressure, and response time. The focus will lie on the most widely used and accepted optodes made by Aanderaa and Sea-Bird. We revisit the essentials and caveats of in-situ in air calibration as well as of time response correction for profiling applications, and provide requirements for a successful field deployment. In addition, all required steps to post-correct oxygen optode data will be discussed. We hope this summary will serve as a comprehensive, yet concise reference to help people get started with oxygen observations, ensure successful sensor deployments and acquisition of highest quality data, and facilitate post-treatment of oxygen data. In the end, we hope that this will lead to more and higher-quality oxygen observations and help to advance our understanding of ocean biogeochemistry in a changing ocean.

Description: Benthic foraminifera from Bottsand coastal lagoon, western Baltic Sea, have been studied since the mid-1960s. They were monitored annually in late autumn since 2003 at the terminal ditch of the lagoon. There were 12 different species recognised, of which three have not been recorded during earlier investigations. Dominant species showed strong interannual fluctuations and a steady increase in population densities over the last decade. Elphidium incertum, a stenohaline species of the Baltic deep water fauna, colonised the Bottsand lagoon in 2016, most likely during a period of salinities 〉19 units and water temperatures of 18 °C on average in early autumn. The high salinities probably triggered their germination from a propagule bank in the ditch bottom sediment. The new E. incertum population showed densities higher by an order of magnitude than those of the indigenous species. The latter did not decline, revealing that E. incertum used another food source or occupied a different microhabitat. Elphidium incertum survived transient periods of lower salinities in late autumn 2017, though with reduced abundances, and became a regular faunal constituent at the Bottsand lagoon.

Description: The quantitative reconstruction of past seawater salinity has yet to be achieved and the search for a direct and independent salinity proxy is ongoing. Recent culture and field studies show a significant positive correlation of Na/Ca with salinity in benthic and planktonic foraminiferal calcite. For accurate paleoceanographic reconstructions, consistent and reliable calibrations are necessary, which are still missing. In order to assess the reliability of foraminiferal Na/Ca as a direct proxy for seawater salinity, this study presents electron microprobe Na/Ca data, measured on cultured specimens of Trilobatus sacculifer. The culture experiments were conducted over a wide salinity range of 26 to 45, while temperature was kept constant. To further understand potential controlling factors of Na incorporation, measurements were also performed on foraminifera cultured at various temperatures in the range of 19.5 °C to 29.5 °C under constant salinity conditions. Foraminiferal Na/Ca ratios positively correlate with seawater salinity (Na/Caforam = 0.97 + 0.115 ⋅ Salinity, R = 0.97, p 〈 0.005). Temperature on the other hand exhibits no statistically significant relationship with Na/Ca ratios indicating salinity to be the dominant factor controlling Na incorporation. The culturing results are corroborated by measurements on T. sacculifer from Caribbean and Gulf of Guinea surface sediments. In conclusion, planktonic foraminiferal Na/Ca can be applied as a reliable proxy for reconstructing sea surface salinities, albeit species-specific calibrations might be necessary.

Description: Increasing interest in deep-sea mineral resources, such as polymetallic nodules, calls for environmental research about possible impacts of mineral exploitation on the deep-sea ecosystem. So far, little geochemical comparisons of deep-sea sediments before and after mining induced disturbances have been made, and thus long-term environmental effects of deep-sea mining are unknown. Here we present geochemical data from sediment cores from an experimental disturbance area at 4,100 m water depth in the Peru Basin. The site was revisited in 2015, 26 years after a disturbance experiment mimicking nodule mining was carried out and compared to sites outside the experimental zone which served as a pre-disturbance reference. We investigated if signs of the disturbance are still visible in the solid phase and the pore water after 26 years or if pre-disturbance conditions have been re-established. Additionally, a new disturbance was created during the cruise and sampled 5 weeks later to compare short- and longer-term impacts. The particulate fraction and pore water were analyzed for major and trace elements to study element distribution and processes in the surface sediment. Pore water and bottom water samples were also analyzed for oxygen, nitrate, dissolved organic carbon, and dissolved amino acids, to examine organic matter degradation processes. The study area of about 11 km2 was found to be naturally more heterogeneous than expected, requiring an analysis of spatial variability before the disturbed and undisturbed sites can be compared. The disturbed sites exhibit various disturbance features: some surface sediments were mixed through, others had the top layer removed and some had additional material deposited on top. Pore water constituents have largely regained pre-disturbance gradients after 26 years. The solid phase, however, shows clear differences between disturbed and undisturbed sites in the top 20 cm so that the impact is still visible in the plowed tracks after 26 years. Especially the upper layer, usually rich in manganese-oxide and associated metals, such as Mo, Ni, Co, and Cu, shows substantial differences in metal distribution. Hence, it can be expected that disturbances from polymetallic nodule mining will have manifold and long-lasting impacts on the geochemistry of the underlying sediment.

Description: We report here the results of total mercury (HgT) determinations along the 2014 Geotraces Geovide cruise (GA01 transect) in the North Atlantic Ocean (NA) from Lisbon (Portugal) to the coast of Labrador (Canada). HgT concentrations in unfiltered samples (HgTUNF) were log-normally distributed and ranged between 0.16 and 1.54 pmol L−1, with a geometric mean of 0.51 pmol L−1 for the 535 samples analysed. The dissolved fraction (〈 0.45 µm) of HgT (HgTF), determined on 141 samples, averaged 78 % of the HgTUNF for the entire data set, 84 % for open seawaters (below 100 m) and 91 % if the Labrador Sea data are excluded, where the primary production was high (with a winter convection down to 1400 m). HgTUNF concentrations increased eastwards and with depth from Greenland to Europe and from subsurface to bottom waters. The HgTUNF concentrations were similarly low in the subpolar gyre waters ( ∼  0.45 pmol L−1), whereas they exceeded 0.60 pmol L−1 in the subtropical gyre waters. The HgTUNF distribution mirrored that of dissolved oxygen concentration, with highest concentration levels associated with oxygen-depleted zones. The relationship between HgTF and the apparent oxygen utilization confirms the nutrient-like behaviour of Hg in the NA. An extended optimum multiparameter analysis allowed us to characterize HgTUNF concentrations in the different source water types (SWTs) present along the transect. The distribution pattern of HgTUNF, modelled by the mixing of SWTs, show Hg enrichment in Mediterranean waters and North East Atlantic Deep Water and low concentrations in young waters formed in the subpolar gyre and Nordic seas. The change in anthropogenic Hg concentrations in the Labrador Sea Water during its eastward journey suggests a continuous decrease in Hg content in this water mass over the last decades. Calculation of the water transport driven by the Atlantic Meridional Overturning Circulation across the Portugal–Greenland transect indicates northward Hg transport within the upper limb and southward Hg transport within the lower limb, with resulting net northward transport of about 97.2 kmol yr−1.

Description: The hydrothermal mats, mounds, and chimneys of the southern Guaymas Basin are the surface expression of complex subsurface hydrothermal circulation patterns. In this overview, we document the most frequently visited features of this hydrothermal area with photographs, temperature measurements, and selected geochemical data; many of these distinct habitats await characterization of their microbial communities and activities. Microprofiler deployments on microbial mats and hydrothermal sediments show their steep geochemical and thermal gradients at millimeter-scale vertical resolution. Mapping these hydrothermal features and sampling locations within the southern Guaymas Basin suggest linkages to underlying shallow sills and heat flow gradients. Recognizing the inherent spatial limitations of much current Guaymas Basin sampling calls for comprehensive surveys of the wider spreading region.

Description: The chemistry–climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parameterizations of aerosols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A 10-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone and CO from IASI and OMI, Aura MLS observations of temperature, HNO3, ClO, and O3 for the evaluation of polar stratospheric processes, an ozonesonde climatology, surface ozone observations from the TOAR database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, OH, NOx, aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NOx emissions are very low, and the impact of the heterogeneous reaction of HNO3 on dust and sea salt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

Description: Marine macrophytes are the foundation of algal forests and seagrass meadows-some of the most productive and diverse coastal marine ecosystems on the planet. These ecosystems provide nursery grounds and food for fish and invertebrates, coastline protection from erosion, carbon sequestration, and nutrient fixation. For marine macrophytes, temperature is generally the most important range limiting factor, and ocean warming is considered the most severe threat among global climate change factors. Ocean warming induced losses of dominant macrophytes along their equatorial range edges, as well as range extensions into polar regions, are predicted and already documented. While adaptive evolution based on genetic change is considered too slow to keep pace with the increasing rate of anthropogenic environmental changes, rapid adaptation may come about through a set of non-genetic mechanisms involving the functional composition of the associated microbiome, as well as epigenetic modification of the genome and its regulatory effect on gene expression and the activity of transposable elements. While research in terrestrial plants demonstrates that the integration of non-genetic mechanisms provide a more holistic picture of a species' evolutionary potential, research in marine systems is lagging behind. Here, we aim to review the potential of marine macrophytes to acclimatize and adapt to major climate change effects via intraspecific variation at the genetic, epigenetic, and microbiome levels. All three levels create phenotypic variation that may either enhance fitness within individuals (plasticity) or be subject to selection and ultimately, adaptation. We review three of the most important phenotypic variations in a climate change context, including physiological variation, variation in propagation success, and in herbivore resistance. Integrating different levels of plasticity, and adaptability into ecological models will allow to obtain a more holistic understanding of trait variation and a realistic assessment of the future performance and distribution of marine macrophytes. Such multi-disciplinary approach that integrates various levels of intraspecific variation, and their effect on phenotypic and physiological variation, is of crucial importance for the effective management and conservation of seagrasses and macroalgae under climate change.

Description: The Earth's mantle convects to lose heat (Holmes, 1931); doing so drives plate tectonics (Turcotte and Oxburgh, 1967). Significant gravitational energy is created by the cooling of oceanic lithosphere atop hotter, less dense mantle. When slabs subduct, this gravitational energy is mostly (~86% for whole mantle flow in a PREM-like mantle) transformed into heat by viscous dissipation. Using this perspective, we reassess the energetics of Earth's mantle. We also reconsider the terrestrial abundances of heat producing elements U, Th, and K, and argue they are lower than previously considered and that consequently the heat produced by radioactive decay within the mantle is comparable to the present-day potential gravitational energy release by subducting slabs—both are roughly ~10–12 TW. We reassess possible core heat flow into the base of the mantle, and determine that the core may be still losing a significant amount of heat from its original formation, potentially more than the radioactive heat generation within the mantle. These factors are all likely to be important for Earth's current energetics, and argue that strong plume-driven upwelling is likely to exist within the convecting mantle.

Description: Lakes and reservoirs play an important role in the carbon cycle, and therefore monitoring their metabolic rates is essential. The triple oxygen-isotope anomaly of dissolved O2 [17Δ =  ln(1+δ17O) − 0.518  ×  ln(1 + δ18O)] offers a new, in situ, perspective on primary production, yet little is known about 17Δ from freshwater systems. We investigated the 17Δ together with the oxygen : argon ratio [Δ(O2 ∕ Ar)] in the subtropical Feitsui Reservoir in Taiwan from June 2014 to July 2015. Here, we present the seasonal variations in 17Δ, GP (gross production), NP (net production) and the NP ∕ GP (net to gross ratio) in association with environmental parameters. The 17Δ varied with depth and season, with values ranging between 26 and 205 per meg. The GP rates were observed to be higher (702 ± 107 mg C m−2 d−1) in winter than those (303 ± 66 mg C m−2 d−1) recorded during the summer. The overall averaged GP was 220 g C m−2 yr−1 and NP was −3 g C m−2 yr−1, implying the reservoir was net heterotrophic on an annual basis. This is due to negative NP rates from October to February (−198 ± 78 mg C m−2 d−1). Comparisons between GP rates obtained from the isotope mass balance approach and 14C bottle incubation method (14C–GP) showed consistent values on the same order of magnitude with a GP ∕ 14C–GP ratio of 1.2 ± 1.1. Finally we noted that, although typhoon occurrences were scarce, higher than average 17Δ values and GP rates were recorded after typhoon events.

Description: Oxygen optode measurements on floats and gliders suffer from a slow time response and various sources of drift in the calibration coefficients. Based on two dual-O2 Argo floats, we show how to post-correct for the effect of the optode's time response and give an update on optode in situ drift stability and in-air calibration. Both floats are equipped with an unpumped Aanderaa 4330 optode and a pumped Sea-Bird SBE63 optode. Response times for the pumped SBE63 were derived following Bittig et al. (2014) and the same methods were used to correct the time response bias. Using both optodes on each float, the time response regime of the unpumped Aanderaa optode was characterized more accurately than previously possible. Response times for the pumped SBE63 on profiling floats are in the range of 25–40 s, while they are between 60 and 95 s for the unpumped 4330 optode. Our parameterization can be employed to post-correct the slow optode time response on floats and gliders. After correction, both sensors agree to within 2–3 µmol kg−1 (median difference) in the strongest gradients (120 µmol kg−1 change over 8 min or 20 dbar) and better elsewhere. However, time response correction is only possible if measurement times are known, i.e., provided by the platform as well as transmitted and stored with the data. The O2 in-air measurements show a significant in situ optode drift of −0.40 and −0.27 % yr−1 over the available 2 and 3 years of deployment, respectively. Optode in-air measurements are systematically biased high during midday surfacings compared to dusk, dawn, and nighttime. While preference can be given to nighttime surfacings to avoid this in-air calibration bias, we suggest a parameterization of the daytime effect as a function of the Sun's elevation to be able to use all data and to better constrain the result. Taking all effects into account, calibration factors have an uncertainty of 0.1 %. In addition, in-air calibration factors vary by 0.1–0.2 % when using different reanalysis models as a reference. The overall accuracy that can be achieved following the proposed correction routines is better than 1 µmol kg−1.

Description: Sponges have a significant impact on marine benthic communities, they are of biotechnological interest owing to their production of bioactive natural compounds, and they promise to provide insights into conserved mechanisms of host–microbe interactions in basal metazoans. The natural variability of sponge-microbe associations across species and environments provides a meaningful ecological and evolutionary framework to investigate animal-microbial symbiosis through experimentation in the field and also in aquaria. In addition, next-generation sequencing technologies have shed light on the genomic repertoire of the sponge host and revealed metabolic capacities and symbiotic lifestyle features of their microbiota. However, our understanding of symbiotic mechanisms is still in its infancy. Here, we discuss the potential and limitations of the sponge-microbe symbiosis as emerging models for animal-associated microbiota.

Description: Superoxide (O−2) is a short lived reactive oxygen species (ROS) formed in seawater by photochemical or biological sources, it is important in the redox cycling of trace elements and organic matter in the ocean. The photoproduction of O−2 is now thought to involve reactions between O2 and reactive reducing (radical) intermediates formed from dissolved organic matter (DOM) via intramolecular reactions between excited singlet state donors and ground-state acceptors (Zhang et al., 2012). In seawater the main pathways identified for the decomposition of O−2 into H2O2 and O2, involve reactions with Cu, Mn, and DOM. In productive regions of the ocean, the reaction between DOM and O−2 can be a significant sink for O−2. Thus, DOM is a key component of both the formation and decomposition of O−2 and formation of H2O2. In the present work we examined the relationships between O−2 decay rates and parameters associated with chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) by using the thermal O−2 source SOTS-1. Filtered samples (0.2 μm) were run both in the presence, and absence, of the metal chelator diethylenetriaminepentaacetic acid (DTPA) to determine the contribution from DOM. Samples were collected along a transect across the continental shelf of the Mauritanian continental shelf during a period of upwelling. In this region we found that reactions with DOM, are a significant sink for O−2 in the Mauritanian Upwelling, constituting on average 58 ± 13% of the O−2 loss rates. Superoxide reactivity with organic matter showed no clear correlation with bulk CDOM or FDOM properties (as assessed by PARAFAC analysis) suggesting that future work should concentrate at the functional group level to clearly elucidate which molecular species are involved as bulk properties represent a wide spread of chemical moieties with different O−2 reactivities. Analysis of FDOM parameters indicates that many of the markers used previously for terrestrial sources of DOM and FDOM are called into question as marine sources exist. In particular recent work (Rico et al., 2013) indicates that algal species may also produce syringic, vanillic, and cinnamic acids, which had previously been ascribed solely to terrestrial vegetation.

Description: Carbohydrates represent an important fraction of labile and semi-labile marine organic matter that is mainly comprised of exopolymeric substances derived from phytoplankton exudation and decay. This study investigates the composition of total combined carbohydrates (tCCHO; 〉1 kDa) and the community development of free-living (0.2–3 μm) and particle-associated (PA) (3–10 μm) bacterioplankton during a spring phytoplankton bloom in the southern North Sea. Furthermore, rates were determined for the extracellular enzymatic hydrolysis that catalyzes the initial step in bacterial organic matter remineralization. Concentrations of tCCHO greatly increased during bloom development, while the composition showed only minor changes over time. The combined concentration of glucose, galactose, fucose, rhamnose, galactosamine, glucosamine, and glucuronic acid in tCCHO was a significant factor shaping the community composition of the PA bacteria. The richness of PA bacteria greatly increased in the post-bloom phase. At the same time, the increase in extracellular β-glucosidase activity was sufficient to explain the observed decrease in tCCHO, indicating the efficient utilization of carbohydrates by the bacterioplankton community during the post-bloom phase. Our results suggest that carbohydrate concentration and composition are important factors in the multifactorial environmental control of bacterioplankton succession and the enzymatic hydrolysis of organic matter during phytoplankton blooms.

Description: Conventional integration of Earth system and ocean models can accrue considerable computational expenses, particularly for marine biogeochemical applications. "Offline" numerical schemes in which only the biogeochemical tracers are time stepped and transported using a pre-computed circulation field can substantially reduce the burden and are thus an attractive alternative. One such scheme is the "transport matrix method" (TMM), which represents tracer transport as a sequence of sparse matrix–vector products that can be performed efficiently on distributed-memory computers. While the TMM has been used for a variety of geochemical and biogeochemical studies, to date the resulting solutions have not been comprehensively assessed against their "online" counterparts. Here, we present a detailed comparison of the two. It is based on simulations of the state-of-the-art biogeochemical sub-model embedded within the widely used coarse-resolution University of Victoria Earth System Climate Model (UVic ESCM). The default, non-linear advection scheme was first replaced with a linear, third-order upwind-biased advection scheme to satisfy the linearity requirement of the TMM. Transport matrices were extracted from an equilibrium run of the physical model and subsequently used to integrate the biogeochemical model offline to equilibrium. The identical biogeochemical model was also run online. Our simulations show that offline integration introduces some bias to biogeochemical quantities through the omission of the polar filtering used in UVic ESCM and in the offline application of time-dependent forcing fields, with high latitudes showing the largest differences with respect to the online model. Differences in other regions and in the seasonality of nutrients and phytoplankton distributions are found to be relatively minor, giving confidence that the TMM is a reliable tool for offline integration of complex biogeochemical models. Moreover, while UVic ESCM is a serial code, the TMM can be run on a parallel machine with no change to the underlying biogeochemical code, thus providing orders of magnitude speed-up over the online model.

Description: The assessment of the ocean biota's role in climate climate change is often carried out with global biogeochemical ocean models that contain many components, and involve a high level of parametric uncertainty. Examination the models' fit to climatologies of inorganic tracers, after the models have been spun up to steady state, is a common, but computationally expensive procedure to assess model performance and reliability. Using new tools that have become available for global model assessment and calibration in steady state, this paper examines two different model types – a complex seven-component model (MOPS), and a very simple two-component model (RetroMOPS) – for their fit to dissolved quantities. Before comparing the models, a subset of their biogeochemical parameters has been optimised against annual mean nutrients and oxygen. Both model types fit the observations almost equally well. The simple model, which contains only nutrients and dissolved organic phosphorus (DOP), is sensitive to the parameterisation of DOP production and decay. The spatio-temporal decoupling of nitrogen and oxygen, and processes involved in their uptake and release, renders oxygen and nitrate valuable tracers for model calibration. In addition, the non-conservative nature of these tracers (with respect to their upper boundary condition) introduces the global bias as a useful additional constraint on model parameters. Dissolved organic phosphorous at the surface behaves antagonistically to phosphate, and suggests that observations of this tracer – although difficult to measure – may be an important asset for model calibration

Description: Benthic microbial methanogenesis is a known source of methane in marine systems. In most sediments, the majority of methanogenesis is located below the sulfate-reducing zone, as sulfate reducers outcompete methanogens for the major substrates hydrogen and acetate. The coexistence of methanogenesis and sulfate reduction has been shown before and is possible through the usage of noncompetitive substrates by methanogens such as methanol or methylated amines. However, knowledge about the magnitude, seasonality, and environmental controls of this noncompetitive methane production is sparse. In the present study, the presence of methanogenesis within the sulfate reduction zone (SRZ methanogenesis) was investigated in sediments (0–30 cm below seafloor, cm b.s.f.) of the seasonally hypoxic Eckernförde Bay in the southwestern Baltic Sea. Water column parameters such as oxygen, temperature, and salinity together with porewater geochemistry and benthic methanogenesis rates were determined in the sampling area "Boknis Eck" quarterly from March 2013 to September 2014 to investigate the effect of seasonal environmental changes on the rate and distribution of SRZ methanogenesis, to estimate its potential contribution to benthic methane emissions, and to identify the potential methanogenic groups responsible for SRZ methanogenesis. The metabolic pathway of methanogenesis in the presence or absence of sulfate reducers, which after the addition of a noncompetitive substrate was studied in four experimental setups: (1) unaltered sediment batch incubations (net methanogenesis), (2) 14C-bicarbonate labeling experiments (hydrogenotrophic methanogenesis), (3) manipulated experiments with the addition of either molybdate (sulfate reducer inhibitor), 2-bromoethanesulfonate (methanogen inhibitor), or methanol (noncompetitive substrate, potential methanogenesis), and (4) the addition of 13C-labeled methanol (potential methylotrophic methanogenesis). After incubation with methanol, molecular analyses were conducted to identify key functional methanogenic groups during methylotrophic methanogenesis. To also compare the magnitudes of SRZ methanogenesis with methanogenesis below the sulfate reduction zone (〉 30 cm b.s.f.), hydrogenotrophic methanogenesis was determined by 14C-bicarbonate radiotracer incubation in samples collected in September 2013. SRZ methanogenesis changed seasonally in the upper 30 cm b.s.f. with rates increasing from March (0.2 nmol cm−3 d−1) to November (1.3 nmol cm−3 d−1) 2013 and March (0.2 nmol cm−3 d−1) to September (0.4 nmol cm−3 d−1) 2014. Its magnitude and distribution appeared to be controlled by organic matter availability, C / N, temperature, and oxygen in the water column, revealing higher rates in the warm, stratified, hypoxic seasons (September–November) compared to the colder, oxygenated seasons (March–June) of each year. The majority of SRZ methanogenesis was likely driven by the usage of noncompetitive substrates (e.g., methanol and methylated compounds) to avoid competition with sulfate reducers, as was indicated by the 1000–3000-fold increase in potential methanogenesis activity observed after methanol addition. Accordingly, competitive hydrogenotrophic methanogenesis increased in the sediment only below the depth of sulfate penetration (〉 30 cm b.s.f.). Members of the family Methanosarcinaceae, which are known for methylotrophic methanogenesis, were detected by PCR using Methanosarcinaceae-specific primers and are likely to be responsible for the observed SRZ methanogenesis. The present study indicates that SRZ methanogenesis is an important component of the benthic methane budget and carbon cycling in Eckernförde Bay. Although its contributions to methane emissions from the sediment into the water column are probably minor, SRZ methanogenesis could directly feed into methane oxidation above the sulfate–methane transition zone.

Description: The balance in microbial net consumption of nitrogen and phosphorus was investigated in samples collected in two mesotrophic coastal environments: the Baltic Sea (Tvärminne field station) and the North Sea (Espegrend field station). For this, we have refined a bioassay based on the response in alkaline phosphatase activity (APA) over a matrix of combinations in nitrogen and phosphorus additions. This assay not only provides information on which element (N or P) is the primary limiting nutrient, but also gives a quantitative estimate for the excess of the secondary limiting element (P+ or N+, respectively), as well as the ratio of balanced net consumption of added N and P over short timescales (days). As expected for a Baltic Sea late spring–early summer situation, the Tvärminne assays (n =  5) indicated N limitation with an average P+ =  0.30 ± 0.10 µM-P, when incubated for 4 days. For short incubations (1–2 days), the Espegrend assays indicated P limitation, but the shape of the response surface changed with incubation time, resulting in a drift in parameter estimates toward N limitation. Extrapolating back to zero incubation time gave P limitation with N+ ≈  0.9 µM-N. The N : P ratio (molar) of nutrient net consumption varied considerably between investigated locations: from 2.3 ± 0.4 in the Tvärminne samples to 13 ± 5 and 32 ± 3 in two samples from Espegrend. Our assays included samples from mesocosm acidification experiments, but statistically significant effects of ocean acidification were not found by this method.

Description: The dichotomy between high microbial abundance (HMA) and low microbial abundance (LMA) sponges has been observed in sponge-microbe symbiosis, although the extent of this pattern remains poorly unknown. We characterized the differences between the microbiomes of HMA (n=19) and LMA (n=17) sponges (575 specimens) present in the Sponge Microbiome Project. HMA sponges were associated with richer and more diverse microbiomes than LMA sponges, as indicated by the comparison of alpha diversity metrics. Microbial community structures differed between HMA and LMA sponges considering Operational Taxonomic Units (OTU) abundances and across microbial taxonomic levels, from phylum to species. The largest proportion of microbiome variation was explained by the host identity. Several phyla, classes, and OTUs were found differentially abundant in either group, which were considered “HMA indicators” and “LMA indicators”. Machine learning algorithms (classifiers) were trained to predict the HMA-LMA status of sponges. Among nine different classifiers, higher performances were achieved by Random Forest trained with phylum and class abundances. Random Forest with optimized parameters predicted the HMA-LMA status of additional 135 sponge species (1,232 specimens) without a priori knowledge. These sponges were grouped in four clusters, from which the largest two were composed of species consistently predicted as HMA (n=44) and LMA (n=74). In summary, our analyses shown distinct features of the microbial communities associated with HMA and LMA sponges. The prediction of the HMA-LMA status based on the microbiome profiles of sponges demonstrates the application of machine learning to explore patterns of host-associated microbial communities.

Description: Redox-sensitive mobilization of nutrients from sediments strongly affects the eutrophic state of the central Baltic Sea; a region associated with the spread of hypoxia and almost permanently anoxic and sulfidic conditions in the deeper basins. Ventilation of these basins depends on renewal by inflow of water enriched in oxygen (O2) from the North Sea, occurring roughly once per decade. Benthic fluxes and water column distributions of dissolved inorganic nitrogen species, phosphate (PO43-), dissolved inorganic carbon (DIC), sulfide (HS-), and total oxygen uptake (TOU) were measured along a depth gradient in the Eastern Gotland Basin (EGB). Campaigns were conducted during euxinic conditions of the deep basin in Aug./Sept. 2013 and after two inflow events in July/Aug. 2015 and March 2016 when O2 concentrations in deep waters reached 60 μM. The intrusion of O2-rich North Sea water into the EGB led to an approximate 33 and 10% reduction of the seabed PO43- and ammonium (NH4+) release from deep basin sediments. Post-inflow, the deep basin sediment was rapidly colonized by HS- oxidizing bacteria tentatively assigned to the family Beggiatoaceae, and HS- release was completely suppressed. The presence of a hypoxic transition zone (HTZ) between 80 and 120 m water depth was confirmed not only for euxinic deep-water conditions during 2013 but also for post-inflow conditions. Because deep-water renewal did not ventilate the HTZ, where PO43- and NH4+ fluxes were highest, high seabed nutrient release there was relatively unchanged. Extrapolation of the in situ nutrient fluxes indicated that, overall, the reduction in PO43- and NH4+ release in response to deep-water renewal can be considered as minor, reducing the internal nutrient load by 2 and 12% only, respectively. Infrequent inflow events thus have a limited capacity to sustainably reduce internal nutrient loading in the EGB and mitigate eutrophication.

Description: Cold-water corals are important bioengineers that provide structural habitat for a diverse species community. About 70% of the presently known scleractinian cold-water corals are expected to be exposed to corrosive waters by the end of this century due to ocean acidification. At the same time, the corals will experience a steady warming of their environment. Studies on the sensitivity of cold-water corals to climate change mainly concentrated on single stressors in short-term incubation approaches, thus not accounting for possible long-term acclimatisation and the interactive effects of multiple stressors. Besides, preceding studies did not test for possible compensatory effects of a change in food availability. In this study a multifactorial long-term experiment (6 months) was conducted with end-of-the-century scenarios of elevated pCO2 and temperature levels in order to examine the acclimatisation potential of the cosmopolitan cold-water coral Lophelia pertusa to future climate change related threats. For the first time multiple ocean change impacts including the role of the nutritional status were tested on L. pertusa with regard to growth, “fitness,” and survival. Our results show that while L. pertusa is capable of calcifying under elevated CO2 and temperature, its condition (fitness) is more strongly influenced by food availability rather than changes in seawater chemistry. Whereas growth rates increased at elevated temperature (+4°C), they decreased under elevated CO2 concentrations (~800 μatm). No difference in net growth was detected when corals were exposed to the combination of increased CO2 and temperature compared to ambient conditions. A 10-fold higher food supply stimulated growth under elevated temperature, which was not observed in the combined treatment. This indicates that increased food supply does not compensate for adverse effects of ocean acidification and underlines the importance of considering the nutritional status in studies investigating organism responses under environmental changes.

Description: Marine researchers continue to create large quantities of benthic images e.g., using AUVs (Autonomous Underwater Vehicles). In order to quantify the size of sessile objects in the images, a pixel-to-centimeter ratio is required for each image, often indirectly provided through a geometric laser point (LP) pattern, projected onto the seafloor. Manual annotation of these LPs in all images is too time-consuming and thus infeasible for nowadays data volumes. Because of the technical evolution of camera rigs, the LP's geometrical layout and color features vary for different expeditions and projects. This makes the application of one algorithm, tuned to a strictly defined LP pattern, also ineffective. Here we present the web-tool DELPHI, that efficiently learns the LP layout for one image transect/collection from just a small number of hand labeled LPs and applies this layout model to the rest of the data. The efficiency in adapting to new data allows to compute the LPs and the pixel-to-centimeter ratio fully automatic and with high accuracy. DELPHI is applied to two real-world examples and shows clear improvements regarding reduction of tuning effort for new LP patterns as well as increasing detection performance.

Description: Nitrous oxide (N2O) is one of the most important greenhouse gases and a major sink for stratospheric ozone. Estuaries are sites of intense biological production and N2O emissions. We aimed to identify hot spots of N2O production and potential pathways contributing to N2O concentrations in the surface water of the tidal Elbe estuary. During two research cruises in April and June 2015, surface water N2O concentrations were measured along the salinity gradient of the Elbe estuary by using a laser-based on-line analyzer coupled to an equilibrator. Based on these high-resolution N2O profiles, N2O saturations, and fluxes across the surface water/atmosphere interface were calculated. Additional measurements of DIN concentrations, oxygen concentration, and salinity were performed. Highest N2O concentrations were determined in the Hamburg port region reaching maximum values of 32.3 nM in April 2015 and 52.2 nM in June 2015. These results identify the Hamburg port region as a significant hot spot of N2O production, where linear correlations of AOU-N2Oxs indicate nitrification as an important contributor to N2O production in the freshwater part. However, in the region with lowest oxygen saturation, sediment denitrification obviously affected water column N2O saturation. The average N2O saturation over the entire estuary was 201% (SD: ±94%), with an average estuarine N2O flux density of 48 μmol m−2 d−1 and an overall emission of 0.18 Gg N2O y−1. In comparison to previous studies, our data indicate that N2O production pathways over the whole estuarine freshwater part have changed from predominant denitrification in the 1980s toward significant production from nitrification in the present estuary. Despite a significant reduction in N2O saturation compared to the 1980s, N2O concentrations nowadays remain on a high level, comparable to the mid-90s, although a steady decrease of DIN inputs occurred over the last decades. Hence, the Elbe estuary still remains an important source of N2O to the atmosphere.

Description: Here we show the use of the 210Pb-226Ra excess method to determine the growth rate of two corals from the world's largest known cold-water coral reef, Røst Reef, north of the Arctic circle off Norway. Colonies of each of the two species that build the reef, Lophelia pertusa and Madrepora oculata, were collected alive at 350 m depth using a submersible. Pb and Ra isotopes were measured along the major growth axis of both specimens using low level alpha and gamma spectrometry and trace element compositions were studied. 210Pb and 226Ra differ in the way they are incorporated into coral skeletons. Hence, to assess growth rates, we considered the exponential decrease of initially incorporated 210Pb, as well as the increase in 210Pb from the decay of 226Ra and contamination with 210Pb associated with Mn-Fe coatings that we were unable to remove completely from the oldest parts of the skeletons. 226Ra activity was similar in both coral species, so, assuming constant uptake of 210Pb through time, we used the 210Pb-226Ra chronology to calculate growth rates. The 45.5 cm long branch of M. oculata was 31 yr with an average linear growth rate of 14.4 ± 1.1 mm yr−1 (2.6 polyps per year). Despite cleaning, a correction for Mn-Fe oxide contamination was required for the oldest part of the colony; this correction corroborated our radiocarbon date of 40 yr and a mean growth rate of 2 polyps yr−1. This rate is similar to the one obtained in aquarium experiments under optimal growth conditions.

Description: Gel particles—a class of abundant transparent organic particles—have increasingly gathered attention in marine research. Field studies on the bacterial colonization of marine gels however are still scarce. So far, most studies on respective particles have focused on the upper ocean, while little is known on their occurrence in the deep sea. Here, we report on the vertical distribution of the two most common gel particle types, which are polysaccharide-containing transparent exopolymer particles (TEP) and proteinaceous Coomassie stainable particles (CSP), as well as numbers of bacteria attached to gel particles throughout the water column, from the surface ocean down to the bathypelagial (〈 3,000 m). Our study was conducted in the Arctic Fram Strait during northern hemispheres' summer in 2015. Besides data on the bacterial colonization of the two gel particle types (TEP and CSP), we present bacterial densities on different gel particle size classes according to 12 different sampling depths at four sampling locations. Gel particles were frequently abundant at all sampled depths, and their concentrations decreased from the euphotic zone to the dark ocean. They were colonized by bacteria at all sampled water depths with risen importance at the deepest water layers, where fractions of bacteria attached to gel particles (%) increased within the total bacterial community. Due to the omnipresent bacterial colonization of gel particles at all sampled depths in our study, we presume that euphotic production of this type of organic matter may affect microbial species distribution within the whole water column in the Fram Strait, down to the deep sea. Our results raise the question if changes in the bacterial community composition and functioning on gel particles occur over depth, which may affect microbial respiration and remineralization rates of respective particles in different water layers.

Description: The Ocean Model Intercomparison Project (OMIP) focuses on the physics and biogeochemistry of the ocean component of Earth system models participating in the sixth phase of the Coupled Model Intercomparison Project (CMIP6). OMIP aims to provide standard protocols and diagnostics for ocean models, while offering a forum to promote their common assessment and improvement. It also offers to compare solutions of the same ocean models when forced with reanalysis data (OMIP simulations) vs. when integrated within fully coupled Earth system models (CMIP6). Here we detail simulation protocols and diagnostics for OMIP's biogeochemical and inert chemical tracers. These passive-tracer simulations will be coupled to ocean circulation models, initialized with observational data or output from a model spin-up, and forced by repeating the 1948–2009 surface fluxes of heat, fresh water, and momentum. These so-called OMIP-BGC simulations include three inert chemical tracers (CFC-11, CFC-12, SF6) and biogeochemical tracers (e.g., dissolved inorganic carbon, carbon isotopes, alkalinity, nutrients, and oxygen). Modelers will use their preferred prognostic BGC model but should follow common guidelines for gas exchange and carbonate chemistry. Simulations include both natural and total carbon tracers. The required forced simulation (omip1) will be initialized with gridded observational climatologies. An optional forced simulation (omip1-spunup) will be initialized instead with BGC fields from a long model spin-up, preferably for 2000 years or more, and forced by repeating the same 62-year meteorological forcing. That optional run will also include abiotic tracers of total dissolved inorganic carbon and radiocarbon, CTabio and 14CTabio, to assess deep-ocean ventilation and distinguish the role of physics vs. biology. These simulations will be forced by observed atmospheric histories of the three inert gases and CO2 as well as carbon isotope ratios of CO2. OMIP-BGC simulation protocols are founded on those from previous phases of the Ocean Carbon-Cycle Model Intercomparison Project. They have been merged and updated to reflect improvements concerning gas exchange, carbonate chemistry, and new data for initial conditions and atmospheric gas histories. Code is provided to facilitate their implementation.

Description: The injection of sulphur into the stratosphere by explosive volcanic eruptions is the cause of significant climate variability. Based on sulphate records from a suite of ice cores from Greenland and Antarctica, the eVolv2k database includes estimates of the magnitudes and approximate source latitudes of major volcanic stratospheric sulphur injection (VSSI) events from 500 BCE to 1900 CE, constituting an update of prior reconstructions and an extension of the record by 1000 years. The VSSI estimates incorporate improvements to the ice core records in terms of synchronization and dating, refinements to the methods used to estimate VSSI from ice core records, and includes first estimates of the random uncertainties in VSSI values. VSSI estimates for many of the largest eruptions, including Samalas (1257), Tambora (1815) and Laki (1783) are within 10% of prior estimates. A number of strong events are included in eVolv2k which are largely underestimated or not included in earlier VSSI reconstructions, including events in 540, 574, 682 and 1108 CE. The long term annual mean VSSI from major volcanic eruptions is estimated to be ∼ 0.5 Tg [S] yr−1, ∼ 50 % greater than a prior reconstruction, due to the identification of more events and an increase in the magnitude of many intermediate events. A long-term, latitudinally and monthly resolved stratospheric aerosol optical depth (SAOD) time series is reconstructed from the eVolv2k VSSI estimates, and the resulting global mean SAOD is found to be similar (within 33%) to a prior reconstruction for most of the largest eruptions. The long-term (500 BCE–900 CE) average global mean SAOD estimated from the eVolv2k VSSI estimates and including a constant "background" injection of stratospheric sulphur is ∼ 0.014, 30 % greater than a prior reconstruction. These new long-term reconstructions of past VSSI and SAOD variability give context to recent volcanic forcing, suggesting that the 20th century was a period of somewhat weaker than average volcanic forcing, with current best estimates of 20th century mean VSSI and SAOD values being 25 and 14 % less, respectively, than the mean of the 500 BCE to 1900 CE period. The reconstructed VSSI and SAOD data are available at https://doi.org/10.1594/WDCC/eVolv2k_v2〉.

Description: The Cretaceous ocean witnessed intervals of profound perturbations such as volcanic input of large amounts of CO2, anoxia, eutrophication and introduction of biologically relevant metals. Some of these extreme events were characterized by size reduction and/or morphological changes of a few calcareous nannofossil species. The correspondence between intervals of high trace metal concentrations and coccolith dwarfism suggests a negative effect of these elements on nannoplankton biocalcification processes in past oceans. In order to test this hypothesis, we explored the potential effect of a mixture of trace metals on growth and morphology of four living coccolithophore species, namely Emiliania huxleyi, Gephyrocapsa oceanica, Pleurochrysis carterae and Coccolithus pelagicus. The phylogenetic history of coccolithophores shows that the selected living species are linked to Mesozoic species showing dwarfism under excess metal concentrations. The trace metals tested were chosen to simulate the environmental stress identified in the geological record and upon known trace metal interactions with living coccolithophore algae. Our laboratory experiments demonstrated that elevated trace metal concentrations, similarly to the fossil record, affect coccolithophore algae size and/or weight. Smaller coccoliths were detected in E. huxleyi and C. pelagicus, while coccoliths of G. oceanica showed a decrease in size only at the highest trace metal concentrations. P. carterae coccolith size was unresponsive to changing trace metal concentrations. These differences among species allow discriminating the most- (P. carterae), intermediate- (E. huxleyi and G. oceanica) and least-tolerant (C. pelagicus) taxa. The fossil record and the experimental results converge on a selective response of coccolithophores to metal availability. These species-specific differences must be considered before morphological features of coccoliths are used to reconstruct paleo-chemical conditions.

Description: The Baltic Sea is a seasonally ice-covered marginal sea in northern Europe with intense wintertime ship traffic and a sensitive ecosystem. Understanding and modeling the evolution of the sea-ice pack is important for climate effect studies and forecasting purposes. Here we present and evaluate the sea-ice component of a new NEMO–LIM3.6-based ocean–sea-ice setup for the North Sea and Baltic Sea region (NEMO-Nordic). The setup includes a new depth-based fast-ice parametrization for the Baltic Sea. The evaluation focuses on long-term statistics, from a 45-year long hindcast, although short-term daily performance is also briefly evaluated. We show that NEMO-Nordic is well suited for simulating the mean sea-ice extent, concentration, and thickness as compared to the best available observational data set. The variability of the annual maximum Baltic Sea ice extent is well in line with the observations, but the 1961–2006 trend is underestimated. Capturing the correct ice thickness distribution is more challenging. Based on the simulated ice thickness distribution we estimate the undeformed and deformed ice thickness and concentration in the Baltic Sea, which compares reasonably well with observations.

Description: We developed a new method for the determination of dissolved nitric oxide (NO) in discrete seawater samples based on the combination of a purge-and-trap setup and a fluorometric detection of NO. 2,3-diaminonaphthalene (DAN) reacts with NO in seawater to form the highly fluorescent 2,3-naphthotriazole (NAT). The fluorescence intensity was linear for NO concentrations in the range from 0.14 to 19 nmol L−1. We determined a detection limit of 0.068 nmol L−1, an average recovery coefficient of 83.8 % (80.2–90.0 %), and a relative standard deviation of ±7.2 %. With our method we determined for the first time the temporal and spatial distributions of NO surface concentrations in coastal waters of the Yellow Sea off Qingdao and in Jiaozhou Bay during a cruise in November 2009. The concentrations of NO varied from below the detection limit to 0.50 nmol L−1 with an average of 0.26 ± 0.14 nmol L−1. NO surface concentrations were generally enhanced significantly during daytime, implying that NO formation processes such as NO2− photolysis are much higher during daytime than chemical NO consumption, which, in turn, lead to a significant decrease in NO concentrations during nighttime. In general, NO surface concentrations and measured NO production rates were higher compared to previously reported measurements. This might be caused by the high NO2− surface concentrations encountered during the cruise. Moreover, additional measurements of NO production rates implied that the occurrence of particles and a temperature increase can enhance NO production rates. With the method introduced here, we have a reliable and comparably easy to use method at hand to measure oceanic NO surface concentrations, which can be used to decipher both its temporal and spatial distributions as well as its biogeochemical pathways in the oceans.

Description: Igneous intrusions in sedimentary basins may have a profound effect on the thermal structure and physical properties of the hosting sedimentary rocks. These include mechanical effects such as deformation and uplift of sedimentary layers, generation of overpressure, mineral reactions and porosity evolution, and fracturing and vent formation following devolatilization reactions and the generation of CO2 and CH4. The gas generation and subsequent migration and venting may have contributed to several of the past climatic changes such as the end-Permian event and the Paleocene-Eocene Thermal Maximum. Additionally, the generation and expulsion of hydrocarbons and cracking of pre-existing oil reservoirs around a hot magmatic intrusion is of significant interest to the energy industry. In this paper, we present a user-friendly 1D FEM based tool, SILLi, which calculates the thermal effects of sill intrusions on the enclosing sedimentary stratigraphy. The model is accompanied by three case studies of sills emplaced in two different sedimentary basins, the Karoo Basin in South Africa and the Vøring Basin offshore Norway. Input data for the model is the present-day well log or sedimentary column with an Excel input file and includes rock parameters such as thermal conductivity, total organic carbon (TOC) content, porosity, and latent heats. The model accounts for sedimentation and burial based on a rate calculated by the sedimentary layer thickness and age. Erosion of the sedimentary column is also included to account for realistic basin evolution. Multiple sills can be emplaced within the system with varying ages. The emplacement of a sill occurs instantaneously. The model can be applied to volcanic sedimentary basins occurring globally. The model output includes the thermal evolution of the sedimentary column through time, and the changes that take place following sill emplacement such as TOC changes, thermal maturity, and the amount of organic and carbonate-derived CO2. The TOC and vitrinite results can be readily benchmarked within the tool to present-day values measured within the sedimentary column. This allows the user to determine the conditions required to obtain results that match observables and leads to a better understanding of metamorphic processes in sedimentary basins.

Description: Past warm periods provide an opportunity to evaluate climate models under extreme forcing scenarios, in particular high ( 〉  800 ppmv) atmospheric CO2 concentrations. Although a post hoc intercomparison of Eocene ( ∼  50  Ma) climate model simulations and geological data has been carried out previously, models of past high-CO2 periods have never been evaluated in a consistent framework. Here, we present an experimental design for climate model simulations of three warm periods within the early Eocene and the latest Paleocene (the EECO, PETM, and pre-PETM). Together with the CMIP6 pre-industrial control and abrupt 4 ×  CO2 simulations, and additional sensitivity studies, these form the first phase of DeepMIP – the Deep-time Model Intercomparison Project, itself a group within the wider Paleoclimate Modelling Intercomparison Project (PMIP). The experimental design specifies and provides guidance on boundary conditions associated with palaeogeography, greenhouse gases, astronomical configuration, solar constant, land surface processes, and aerosols. Initial conditions, simulation length, and output variables are also specified. Finally, we explain how the geological data sets, which will be used to evaluate the simulations, will be developed.

Description: The Stratospheric Sulfur and its Role in Climate (SSiRC) interactive stratospheric aerosol model intercomparison project (ISA-MIP) explores uncertainties in the processes that connect volcanic emission of sulphur gas species and the radiative forcing associated with the resulting enhancement of the stratospheric aerosol layer. The central aim of ISA-MIP is to constrain and improve interactive stratospheric aerosol models and reduce uncertainties in the stratospheric aerosol forcing by comparing results of standardized model experiments with a range of observations. In this paper we present 4 co-ordinated inter-model experiments designed to investigate key processes which influence the formation and temporal development of stratospheric aerosol in different time periods of the observational record. The "Background" (BG) experiment will focus on microphysics and transport processes under volcanically quiescent conditions, when the stratospheric aerosol is controlled by the transport of aerosols and their precursors from the troposphere to the stratosphere. The "Transient Aerosol Record" (TAR) experiment will explore the role of small- to moderate-magnitude volcanic eruptions, anthropogenic sulphur emissions and transport processes over the period 1998–2012 and their role in the warming hiatus. Two further experiments will investigate the stratospheric sulphate aerosol evolution after major volcanic eruptions. The "Historical Eruptions SO2 Emission Assessment" (HErSEA) experiment will focus on the uncertainty in the initial emission of recent large-magnitude volcanic eruptions, while the "Pinatubo Emulation in Multiple models" (PoEMS) experiment will provide a comprehensive uncertainty analysis of the radiative forcing from the 1991 Mt. Pinatubo eruption.

Description: Shorelines exhibit long-range dependence (LRD) and have been shown in some environments to be described in the wavenumber domain by a power law characteristic of scale-independence. Recent evidence suggests that the geomorphology of barrier islands can, however, exhibit scale dependence as a result of systematic variations of the underlying framework geology. The LRD of framework geology, which influences island geomorphology and its response to storms and sea level rise, has not been previously examined. Electromagnetic induction (EMI) surveys conducted along Padre Island National Seashore (PAIS), Texas, USA, reveal that the EMI apparent conductivity σa signal and, by inference, the framework geology exhibits LRD at scales up to 101 to 102 km. Our study demonstrates the utility of describing EMI σa and LiDAR spatial series by a fractional auto-regressive integrated moving average process that specifically models LRD. This method offers a robust and compact way for quantifying the geological variations along a barrier island shoreline using three parameters (p,d,q). We discuss how ARIMA (0,d,0) models that use a single parameter d provide a quantitative measure for determining free and forced barrier island evolutionary behavior across different scales. Statistical analyses at regional, intermediate, and local scales suggest that the geologic framework within an area of paleo-channels exhibits a first order control on dune height. The exchange of sediment amongst nearshore, beach and dune in areas outside this region are scale-independent, implying that barrier islands like PAIS exhibit a combination of free and forced behaviors that affect the response of the island to sea level rise.

Description: Two different photosystems for performing bacteriochlorophyll-mediated photosynthetic energy conversion are employed in different bacterial phyla. Those bacteria employing a photosystem II type of photosynthetic apparatus include the phototrophic purple bacteria (Proteobacteria), Gemmatimonas and Chloroflexus with their photosynthetic relatives. The proteins of the photosynthetic reaction center PufL and PufM are essential components and are common to all bacteria with a type-II photosynthetic apparatus, including the anaerobic as well as the aerobic phototrophic Proteobacteria. Therefore, PufL and PufM proteins and their genes are perfect tools to evaluate the phylogeny of the photosynthetic apparatus and to study the diversity of the bacteria employing this photosystem in nature. Almost complete pufLM gene sequences and the derived protein sequences from 152 type strains and 45 additional strains of phototrophic Proteobacteria employing photosystem II were compared. The results give interesting and comprehensive insights into the phylogeny of the photosynthetic apparatus and clearly define Chromatiales, Rhodobacterales, Sphingomonadales as major groups distinct from other Alphaproteobacteria, from Betaproteobacteria and from Caulobacterales (Brevundimonas subvibrioides). A special relationship exists between the PufLM sequences of those bacteria employing bacteriochlorophyll b instead of bacteriochlorophyll a. A clear phylogenetic association of aerobic phototrophic purple bacteria to anaerobic purple bacteria according to their PufLM sequences is demonstrated indicating multiple evolutionary lines from anaerobic to aerobic phototrophic purple bacteria. The impact of pufLM gene sequences for studies on the environmental diversity of phototrophic bacteria is discussed and the possibility of their identification on the species level in environmental samples is pointed out. © 2018 Imhoff, Rahn, Künzel and Neulinger.

Description: The influence of mesoscale eddies on the flow field and the water masses, especially the oxygen distribution of the eastern tropical South Pacific, is investigated from a mooring, float, and satellite data set. Two anticyclonic (ACE1/2), one mode-water (MWE), and one cyclonic eddy (CE) are identified and followed in detail with satellite data on their westward transition with velocities of 3.2 to 6.0cms−1 from their generation region, the shelf of the Peruvian and Chilean upwelling regime, across the Stratus Ocean Reference Station (ORS;  ∼ 20°S, 85°W) to their decaying region far west in the oligotrophic open ocean. The ORS is located in the transition zone between the oxygen minimum zone and the well oxygenated South Pacific subtropical gyre. Velocity, hydrographic, and oxygen measurements at the mooring show the impact of eddies on the weak flow region of the eastern tropical South Pacific. Strong anomalies are related to the passage of eddies and are not associated with a seasonal signal in the open ocean. The mass transport of the four observed eddies across 85°W is between 1.1 and 1.8Sv. The eddy type-dependent available heat, salt, and oxygen anomalies are 8.1×1018J (ACE2), 1.0×1018J (MWE), and −8.9×1018J (CE) for heat; 25.2×1010kg (ACE2), −3.1×1010kg (MWE), and −41.5×1010kg (CE) for salt; and −3.6×1016µmol (ACE2), −3.5×1016µmol (MWE), and −6.5×1016µmol (CE) for oxygen showing a strong imbalance between anticyclones and cyclones for salt transports probably due to seasonal variability in water mass properties in the formation region of the eddies. Heat, salt, and oxygen fluxes out of the coastal region across the ORS region in the oligotrophic open South Pacific are estimated based on these eddy anomalies and on eddy statistics (gained out of 23 years of satellite data). Furthermore, four profiling floats were trapped in the ACE2 during its westward propagation between the formation region and the open ocean, which allows for conclusions on lateral mixing of water mass properties with time between the core of the eddy and the surrounding water. The strongest lateral mixing was found between the seasonal thermocline and the eddy core during the first half of the eddy lifetime.

Description: The eruption of Mt. Tambora in 1815 was the largest volcanic eruption of the past 500 years. The eruption had significant climatic impacts, leading to the 1816 "year without a summer", and remains a valuable event from which to understand the climatic effects of large stratospheric volcanic sulfur dioxide injections. The eruption also resulted in one of the strongest and most easily identifiable volcanic sulfate signals in polar ice cores, which are widely used to reconstruct the timing and atmospheric sulfate loading of past eruptions. As part of the Model Intercomparison Project on the climatic response to Volcanic forcing (VolMIP), five state-of-the-art global aerosol models simulated this eruption. We analyse both simulated background (no Tambora) and volcanic (with Tambora) sulfate deposition to polar regions and compare to ice core records. The models simulate overall similar patterns of background sulfate deposition, al-though there are differences in regional details and magnitude. However, the volcanic sulfate deposition varies considerably between the models with differences in timing, spatial pattern and magnitude. Mean simulated deposited sulfate on Antarctica ranges from 19 to 264 kgkm-2 and on Greenland from 31 to 194 kgkm-2, as compared to the mean ice-corederived estimates of roughly 50 kgkm-2 for both Greenland and Antarctica. The ratio of the hemispheric atmospheric sulfate aerosol burden after the eruption to the average ice sheet deposited sulfate varies between models by up to a factor of 15. Sources of this inter-model variability include differences in both the formation and the transport of sulfate aerosol. Our results suggest that deriving relationships between sulfate deposited on ice sheets and atmospheric sulfate burdens from model simulations may be associated with greater uncertainties than previously thought.

Description: Oceanic very short-lived substances (VSLSs), such as bromoform (CHBr3), contribute to stratospheric halogen loading and, thus, to ozone depletion. However, the amount, timing, and region of bromine delivery to the stratosphere through one of the main entrance gates, the Indian summer monsoon circulation, are still uncertain. In this study, we created two bromoform emission inventories with monthly resolution for the tropical Indian Ocean and west Pacific based on new in situ bromoform measurements and novel ocean biogeochemistry modeling. The mass transport and atmospheric mixing ratios of bromoform were modeled for the year 2014 with the particle dispersion model FLEXPART driven by ERA-Interim reanalysis. We compare results between two emission scenarios: (1) monthly averaged and (2) annually averaged emissions. Both simulations reproduce the atmospheric distribution of bromoform from ship- and aircraft-based observations in the boundary layer and upper troposphere above the Indian Ocean reasonably well. Using monthly resolved emissions, the main oceanic source regions for the stratosphere include the Arabian Sea and Bay of Bengal in boreal summer and the tropical west Pacific Ocean in boreal winter. The main stratospheric injection in boreal summer occurs over the southern tip of India associated with the high local oceanic sources and strong convection of the summer monsoon. In boreal winter more bromoform is entrained over the west Pacific than over the Indian Ocean. The annually averaged stratospheric injection of bromoform is in the same range whether using monthly averaged or annually averaged emissions in our Lagrangian calculations. However, monthly averaged emissions result in the highest mixing ratios within the Asian monsoon anticyclone in boreal summer and above the central Indian Ocean in boreal winter, while annually averaged emissions display a maximum above the west Indian Ocean in boreal spring. In the Asian summer monsoon anticyclone bromoform atmospheric mixing ratios vary by up to 50% between using monthly averaged and annually averaged oceanic emissions. Our results underline that the seasonal and regional stratospheric bromine injection from the tropical Indian Ocean and west Pacific critically depend on the seasonality and spatial distribution of the VSLS emissions.

Description: The calcareous tubeworm Spirorbis spirorbis is a widespread serpulid species in the Baltic Sea, where it commonly grows as an epibiont on brown macroalgae (genus Fucus). It lives within a Mg-calcite shell and could be affected by ocean acidification and temperature rise induced by the predicted future atmospheric CO2 increase. However, Spirorbis tubes grow in a chemically modified boundary layer around the algae, which may mitigate acidification. In order to investigate how increasing temperature and rising pCO2 may influence S. spirorbis shell growth we carried out four seasonal experiments in the Kiel Outdoor Benthocosms at elevated pCO2 and temperature conditions. Compared to laboratory batch culture experiments the benthocosm approach provides a better representation of natural conditions for physical and biological ecosystem parameters, including seasonal variations. We find that growth rates of S. spirorbis are significantly controlled by ontogenetic and seasonal effects. The length of the newly grown tube is inversely related to the initial diameter of the shell. Our study showed no significant difference of the growth rates between ambient atmospheric and elevated (1100 ppm) pCO2 conditions. No influence of daily average CaCO3 saturation state on the growth rates of S. spirorbis was observed. We found, however, net growth of the shells even in temporarily undersaturated bulk solutions, under conditions that concurrently favoured selective shell surface dissolution. The results suggest an overall resistance of S. spirorbis growth to acidification levels predicted for the year 2100 in the Baltic Sea. In contrast, S. spirorbis did not survive at mean seasonal temperatures exceeding 24 °C during the summer experiments. In the autumn experiments at ambient pCO2, the growth rates of juvenile S. spirorbis were higher under elevated temperature conditions. The results reveal that S. spirorbis may prefer moderately warmer conditions during their early life stages but will suffer from an excessive temperature increase and from increasing shell corrosion as a consequence of progressing ocean acidification.

Description: n the Paris Agreement in 2015 countries agreed on holding global mean surface air warming to "well below 2 degrees C above pre-industrial" levels, but the emission reduction pledges under that agreement are not ambitious enough to meet this target. Therefore, the question arises of whether restoring global warming to this target after exceeding it by artificially removing CO2 from the atmosphere is possible. One important aspect is the reversibility of ocean heat uptake and associated sea level rise, which have very long (centennial to millennial) response timescales. In this study the response of sea level rise due to thermal expansion to a 1% yearly increase of atmospheric CO2 up to a quadrupling of the pre-industrial concentration followed by a 1% yearly decline back to the pre-industrial CO2 concentration is examined using the University of Victoria Earth System Climate Model (UVic ESCM). We find that global mean thermosteric sea level (GMTSL) continues to rise for several decades after atmospheric CO2 starts to decline and does not return to pre-industrial levels for over 1000 years after atmospheric CO2 is restored to the pre-industrial concentration. This finding is independent of the strength of vertical sub-grid-scale ocean mixing implemented in the model. Furthermore, GMTSL rises faster than it declines in response to a symmetric rise and decline in atmospheric CO2 concentration partly because the deep ocean continues to warm for centuries after atmospheric CO2 returns to the pre-industrial concentration. Both GMTSL rise and decline rates increase with increasing vertical ocean mixing. Exceptions from this behaviour arise if the overturning circulations in the North Atlantic and Southern Ocean intensify beyond pre-industrial levels in model versions with lower vertical mixing, which leads to rapid cooling of the deep ocean.

Description: The maintenance and resilience of host-associated microbiota during development is a fundamental process influencing the fitness of many organisms. Several host properties were identified as influencing factors on bacterial colonization, including the innate immune system, mucus composition and diet. In contrast, the importance of bacteria-bacteria interactions on host colonization is less understood. Here, we use bacterial abundance data of the marine model organism Nematostella vectensis to reconstruct potential bacteria-bacteria interactions through co-occurrence networks. The analysis indicates that bacteria-bacteria interactions are dynamic during host colonization and change according to the host’s developmental stage. To assess the predictive power of inferred interactions, we tested bacterial isolates with predicted cooperative or competitive behavior for their ability to influence bacterial recolonization dynamics. Within three days of recolonization all tested bacterial isolates affected bacterial community structure, while only competitive bacteria increased bacterial diversity. Already one week after recolonization almost no differences in bacterial community structure could be observed between control and treatments. These results show that predicted competitive bacteria can influence community structure for a short period of time, verifying the in silico predictions. However, within one week, the effects of the bacterial isolates are neutralized, indicating a high degree of resilience of the bacterial community. Hanna Domin1, Yazmín H. Zurita-Gutiérrez2, Marco Scotti3, Jann Buttlar1, Ute Hentschel Humeida2 and Sebastian Fraune1*

Description: Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, δ13 C, δ15 N, δ18 O, δ30 Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies.

Description: The surface microlayer (SML) is the uppermost thin layer of the ocean and influencing interactions between the air and sea, such as gas exchange, atmospheric deposition and aerosol emission. Organic matter (OM) plays a key role in air-sea exchange processes, but studying how the accumulation of organic compounds in the SML relates to biological processes is impeded in the field by a changing physical environment, in particular wind speed and wave breaking. Here, we studied OM dynamics in the SML under controlled physical conditions in a large annular wind wave channel, filled with natural seawater, over a period of 26 days. Biology in both SML and bulk water was dominated by bacterioneuston and -plankton, respectively, while autotrophic biomass in the two compartments was very low. In general, SML thickness was related to the concentration of dissolved organic carbon (DOC) but not to enrichment of DOC or of specific OM components in the SML. Pronounced changes in OM enrichment and molecular composition were observed in the course of the study and correlated significantly to bacterial abundance. Thereby, hydrolysable amino acids, in particular arginine, were more enriched in the SML than combined carbohydrates. Amino acid composition indicated that less degraded OM accumulated preferentially in the SML. A strong correlation was established between the amount of surfactants coverage and γ-aminobutric acid, suggesting that microbial cycling of amino acids can control physiochemical traits of the SML. Our study shows that accumulation and cycling of OM in the SML can occur independently of recent autotrophic production, indicating a widespread biogenic control of process across the air-sea exchange.

Description: A Catalogue of Marine Biodiversity Indicators was developed with the aim of providing the basis for assessing the environmental status of the marine ecosystems. Useful for the implementation of the Marine Strategy Framework Directive (MSFD), this catalogue allows the navigation of a database of indicators mostly related to biological diversity, non-indigenous species, food webs, and seafloor integrity. Over 600 indicators were compiled, which were developed and used in the framework of different initiatives (e.g., EU policies, research projects) and in national and international contexts (e.g., Regional Seas Conventions, and assessments in non-European seas). The catalogue reflects the current scientific capability to address environmental assessment needs by providing a broad coverage of the most relevant indicators for marine biodiversity and ecosystem integrity. The available indicators are reviewed according to their typology, data requirements, development status, geographical coverage, relevance to habitats or biodiversity components, and related human pressures. Through this comprehensive overview, we discuss the potential of the current set of indicators in a wide range of contexts, from large-scale to local environmental programs, and we also address shortcomings in light of current needs. Developed by the DEVOTES Project, the catalogue is freely available through the DEVOTool software application, which provides browsing and query options for the associated metadata. The tool allows extraction of ranked indicator lists best fulfilling selected criteria, enabling users to search for suitable indicators to address a particular biodiversity component, ecosystem feature, habitat, or pressure in a marine area of interest. This tool is useful for EU Member States, Regional Sea Conventions, the European Commission, non-governmental organizations, managers, scientists, and any person interested in marine environmental assessment. It allows users to build, complement or adjust monitoring programs and has the potential to improve comparability and foster transfer of knowledge across marine regions.

Description: The climate research community uses atmospheric reanalysis data sets to understand a wide range of processes and variability in the atmosphere, yet different reanalyses may give very different results for the same diagnostics. The Stratosphere–troposphere Processes And their Role in Climate (SPARC) Reanalysis Intercomparison Project (S-RIP) is a coordinated activity to compare reanalysis data sets using a variety of key diagnostics. The objectives of this project are to identify differences among reanalyses and understand their underlying causes, to provide guidance on appropriate usage of various reanalysis products in scientific studies, particularly those of relevance to SPARC, and to contribute to future improvements in the reanalysis products by establishing collaborative links between reanalysis centres and data users. The project focuses predominantly on differences among reanalyses, although studies that include operational analyses and studies comparing reanalyses with observations are also included when appropriate. The emphasis is on diagnostics of the upper troposphere, stratosphere, and lower mesosphere. This paper summarizes the motivation and goals of the S-RIP activity and extensively reviews key technical aspects of the reanalysis data sets that are the focus of this activity. The special issue "The SPARC Reanalysis Intercomparison Project (S-RIP)" in this journal serves to collect research with relevance to the S-RIP in preparation for the publication of the planned two (interim and full) S-RIP reports.

Description: Monthly time-series data (1998–2009) of bottom water oxygen, nitrate and nitrite concentrations from the outer shelf (150 m water depth) in the oxygen minimum zone offshore Peru were coupled to a layered biogeochemical sediment model to investigate benthic-pelagic coupling over multi-annual time scales. The model includes the mineralization of four reactive pools of particulate organic carbon (POC) with lifetimes of 0.13, 1.3, 20, and 1700 year that were constrained using empirical data. Total POC rain rates to the seafloor were derived from satellite based estimates of primary production. Solute fluxes and concentrations in sediment porewater showed highly dynamic behavior over the course of a typical year. Conversion of fixed N to N2 by denitrification varied from 1.1 mmol m−2 d−1 of N in winter to 1.8 mmol m−2 d−1 of N in summer with a long term mean N loss for the shelf of 1.5 mmol m−2 d−1 of N. Fixed N loss across the whole time-series agreed very well with a previously-published vertically-integrated sediment model for coupling the benthic and pelagic N cycle in regional and global models. Dissimilatory nitrate reduction to ammonium (DNRA) emerges as a major process in the benthic N cycle, producing on average 1.9 mmol m−2 d−1 of ammonium: more than twice the rate of ammonification of organic nitrogen. The model predicts sulfide emissions from the sediment of up to 1 mmol m−2 d−1 when POC rain rate exceeds 20 mmol m−2 d−1, in agreement with past observations of benthic sulfide fluxes and sulfide plume distributions in the water column. This study demonstrates that sediments on the Peruvian shelf are not static repositories that are independent of changes taking place in the water column. Our results strongly suggest the shelf sediments must exert an important feedback on biogeochemical processes in the overlying waters, and should be considered in regional model studies.

Description: A high-resolution dynamical model (Nucleus for European Modelling of the Ocean, Mediterranean configuration – NEMO-MED12) was used to give the first simulation of the distribution of radiocarbon (14C) across the whole Mediterranean Sea. The simulation provides a descriptive overview of both the natural pre-bomb 14C and the entire anthropogenic radiocarbon transient generated by the atmospheric bomb tests performed in the 1950s and early 1960s. The simulation was run until 2011 to give the post-bomb distribution. The results are compared to available in situ measurements and proxy-based reconstructions. The radiocarbon simulation allows an additional and independent test of the dynamical model, NEMO-MED12, and its performance to produce the thermohaline circulation and deep-water ventilation. The model produces a generally realistic distribution of radiocarbon when compared with available in situ data. The results demonstrate the major influence of the flux of Atlantic water through the Strait of Gibraltar on the inter-basin natural radiocarbon distribution and characterize the ventilation of intermediate and deep water especially through the propagation of the anthropogenic radiocarbon signal. We explored the impact of the interannual variability on the radiocarbon distribution during the Eastern Mediterranean Transient (EMT) event. It reveals a significant increase in 14C concentration (by more than 60 ‰) in the Aegean deep water and at an intermediate level (value up to 10 ‰) in the western basin. The model shows that the EMT makes a major contribution to the accumulation of radiocarbon in the eastern Mediterranean deep waters.

Description: Bacterial cell–cell communication (quorum sensing, QS) represents a fundamental process crucial for biofilm formation, pathogenicity, and virulence allowing coordinated, concerted actions of bacteria depending on their cell density. With the widespread appearance of antibiotic-resistance of biofilms, there is an increasing need for novel strategies to control harmful biofilms. One attractive and most likely effective approach is to target bacterial communication systems for novel drug design in biotechnological and medical applications. In this study, metagenomic large-insert libraries were constructed and screened for QS interfering activities (quorum quenching, QQ) using recently established reporter strains. Overall, 142 out of 46,400 metagenomic clones were identified to interfere with acyl-homoserine lactones (AHLs), 13 with autoinducer-2 (AI-2). Five cosmid clones with highest simultaneous interfering activities were further analyzed and the respective open reading frames conferring QQ activities identified. Those showed homologies to bacterial oxidoreductases, proteases, amidases and aminotransferases. Evaluating the ability of the respective purified QQ-proteins to prevent biofilm formation of several model systems demonstrated highest inhibitory effects of QQ-2 using the crystal violet biofilm assay. This was confirmed by heterologous expression of the respective QQ proteins in Klebsiella oxytoca M5a1 and monitoring biofilm formation in a continuous flow cell system. Moreover, QQ-2 chemically immobilized to the glass surface of the flow cell effectively inhibited biofilm formation of K. oxytoca as well as clinical K. pneumoniae isolates derived from patients with urinary tract infections. Indications were obtained by molecular and biochemical characterizations that QQ-2 represents an oxidoreductase most likely reducing the signaling molecules AHL and AI-2 to QS-inactive hydroxy-derivatives. Overall, we propose that the identified novel QQ-2 protein efficiently inhibits AI-2 modulated biofilm formation by modifying the signal molecule; and thus appears particularly attractive for medical and biotechnological applications.

Description: Anaerobic microbial hydrocarbon degradation is a major biogeochemical process at marine seeps. Here we studied the response of the microbial community to petroleum seepage simulated for 190 days in a sediment core from the Caspian Sea using a sediment-oil-flow-through (SOFT) system. Untreated (without simulated petroleum seepage) and SOFT sediment microbial communities shared 43% bacterial genuslevel 16S rRNA-based operational taxonomic units (OTU0:945) but shared only 23% archaeal OTU0:945. The community differed significantly between sediment layers. The detection of fourfold higher deltaproteobacterial cell numbers in SOFT than in untreated sediment at depths characterized by highest sulfate reduction rates and strongest decrease of gaseous and mid-chain alkane concentrations indicated a specific response of hydrocarbon-degrading Deltaproteobacteria. Based on an increase in specific CARD-FISH cell numbers, we suggest the following groups of sulfate-reducing bacteria to be likely responsible for the observed decrease in aliphatic and aromatic hydrocarbon concentration in SOFT sediments: clade SCA1 for propane and butane degradation, clade LCA2 for mid- to long-chain alkane degradation, clade Cyhx for cycloalkanes, pentane and hexane degradation, and relatives of Desulfobacula for toluene degradation. Highest numbers of archaea of the genus Methanosarcina were found in the methanogenic zone of the SOFT core where we detected preferential degradation of long-chain hydrocarbons. Sequencing of masD, a marker gene for alkane degradation encoding (1-methylalkyl)succinate synthase, revealed a low diversity in SOFT sediment with two abundant species-level MasD OTU0:96.

Description: Cold-water coral (CWC) reefs are heterogeneous ecosystems comprising numerous microhabitats. A typical European CWC reef provides various biogenic microhabitats (within, on and surrounding colonies of coral species such as Lophelia pertusa, Paragorgia arborea and Primnoa resedaeformis, or formed by their remains after death). These microhabitats may be surrounded and intermixed with non-biogenic microhabitats (soft sediment, hard ground, gravel/pebbles, steep walls). To date, studies of distribution of sessile fauna across CWC reefs have been more numerous than those investigating mobile fauna distribution. In this study we quantified shrimp densities associated with key CWC microhabitat categories at the Røst Reef, Norway, by analysing image data collected by towed video sled in June 2007. We also investigated shrimp distribution patterns on the local scale (〈40 cm) and how these may vary with microhabitat. Shrimp abundances at the Røst Reef were on average an order of magnitude greater in biogenic reef microhabitats than in non-biogenic microhabitats. Greatest shrimp densities were observed in association with live Paragorgia arborea microhabitat (43 shrimp m−2, SD = 35.5), live Primnoa resedaeformis microhabitat (41.6 shrimp m−2, SD = 26.1) and live Lophelia pertusa microhabitat (24.4 shrimp m−2, SD = 18.6). In non-biogenic microhabitat, shrimp densities were 〈2 shrimp m−2. CWC reef microhabitats appear to support greater shrimp densities than the surrounding non-biogenic microhabitats at the Røst Reef, at least at the time of survey.

Description: Extensive biogeochemical transformation of organic matter takes place in the shallow continental shelf seas of Siberia. This, in combination with brine production from sea-ice formation, results in cold bottom waters with relatively high salinity and nutrient concentrations, as well as low oxygen and pH levels. Data from the SWERUS-C3 expedition with icebreaker Oden, from July to September 2014, show the distribution of such nutrient-rich, cold bottom waters along the continental margin from about 140 to 180° E. The water with maximum nutrient concentration, classically named the upper halocline, is absent over the Lomonosov Ridge at 140° E, while it appears in the Makarov Basin at 150° E and intensifies further eastwards. At the intercept between the Mendeleev Ridge and the East Siberian continental shelf slope, the nutrient maximum is still intense, but distributed across a larger depth interval. The nutrient-rich water is found here at salinities of up to ∼ 34.5, i.e. in the water classically named lower halocline. East of 170° E transient tracers show significantly less ventilated waters below about 150 m water depth. This likely results from a local isolation of waters over the Chukchi Abyssal Plain as the boundary current from the west is steered away from this area by the bathymetry of the Mendeleev Ridge. The water with salinities of ∼ 34.5 has high nutrients and low oxygen concentrations as well as low pH, typically indicating decay of organic matter. A deficit in nitrate relative to phosphate suggests that this process partly occurs under hypoxia. We conclude that the high nutrient water with salinity ∼ 34.5 are formed on the shelf slope in the Mendeleev Ridge region from interior basin water that is trapped for enough time to attain its signature through interaction with the sediment.

Description: Nitrogen is a key limiting nutrient that influences marine productivity and carbon sequestration in the ocean via the biological pump. In this study, we present the first estimates of nitrogen cycling in a coupled 3D ocean-biogeochemistry-isotope model forced with realistic boundary conditions from the Last Glacial Maximum (LGM) ~21,000 years before present constrained by nitrogen isotopes. The model predicts a large decrease in nitrogen loss rates due to higher oxygen concentrations in the thermocline and sea level drop, and, as a response, reduced nitrogen fixation. Model experiments are performed to evaluate effects of hypothesized increases of atmospheric iron fluxes and oceanic phosphorus inventory relative to present-day conditions. Enhanced atmospheric iron deposition, which is required to reproduce observations, fuels export production in the Southern Ocean causing increased deep ocean nutrient storage. This reduces transport of preformed nutrients to the tropics via mode waters, thereby decreasing productivity, oxygen deficient zones, and water column N-loss there. A larger global phosphorus inventory up to 15% cannot be excluded from the currently available nitrogen isotope data. It stimulates additional nitrogen fixation that increases the global oceanic nitrogen inventory, productivity, and water column N-loss. Among our sensitivity simulations, the best agreements with nitrogen isotope data from LGM sediments indicate that water column and sedimentary N-loss were reduced by 17–62% and 35–69%, respectively, relative to preindustrial values. Our model demonstrates that multiple processes alter the nitrogen isotopic signal in most locations, which creates large uncertainties when quantitatively constraining individual nitrogen cycling processes. One key uncertainty is nitrogen fixation, which decreases by 25–65% in the model during the LGM mainly in response to reduced N-loss, due to the lack of observations in the open ocean most notably in the tropical and subtropical southern hemisphere. Nevertheless, the model estimated large increase to the global nitrate inventory of 6.5–22% suggests it may play an important role enhancing the biological carbon pump that contributes to lower atmospheric CO2 during the LGM.

Description: Despite the huge extent of the ocean's surface, until now relatively little attention has been paid to the sea surface microlayer (SML) as the ultimate interface where heat, momentum and mass exchange between the ocean and the atmosphere takes place. Via the SML, large-scale environmental changes in the ocean such as warming, acidification, deoxygenation, and eutrophication potentially influence cloud formation, precipitation, and the global radiation balance. Due to the deep connectivity between biological, chemical, and physical processes, studies of the SML may reveal multiple sensitivities to global and regional changes. Understanding the processes at the ocean's surface, in particular involving the SML as an important and determinant interface, could therefore provide an essential contribution to the reduction of uncertainties regarding ocean-climate feedbacks. This review identifies gaps in our current knowledge of the SML and highlights a need to develop a holistic and mechanistic understanding of the diverse biological, chemical, and physical processes occurring at the ocean-atmosphere interface. We advocate the development of strong interdisciplinary expertise and collaboration in order to bridge between ocean and atmospheric sciences. Although this will pose significant methodological challenges, such an initiative would represent a new role model for interdisciplinary research in Earth System sciences.

Description: Submarine canyons are known as one of the seafloor morphological features where living cold-water coral (CWC) communities develop in the Mediterranean Sea. We investigated the CWC community of the two westernmost submarine canyons of the Gulf of Lions canyon system: the Cap de Creus Canyon (CCC) and Lacaze-Duthiers Canyon (LDC). Coral associations have been studied through video material recorded by means of a manned submersible and a remotely operated vehicle. Video transects have been conducted and analyzed in order to obtain information on (1) coral bathymetric distribution and density patterns, (2) size structure of coral populations, and (3) coral colony position with respect to the substrate. Madrepora oculata was the most abundant CWC in both canyons, while Lophelia pertusa and Dendrophyllia cornigera mostly occurred as isolated colonies or in small patches. An important exception was detected in a vertical cliff in LDC where a large L. pertusa framework was documented. This is the first record of such an extended L. pertusa framework in the Mediterranean Sea. In both canyons coral populations were dominated by medium and large colonies, but the frequent presence of small-sized colonies also indicate active recruitment. The predominant coral orientation (90° and 135°) is probably driven by the current regime as well as by the sediment load transported by the current flows. In general, no clear differences were observed in the abundance and in the size structure of the CWC populations between CCC and LDC, despite large differences in particulate matter between canyons.

Description: As a major source for atmospheric CO2, the Peruvian upwelling region exhibits strong variability in surface fCO2 on short spatial and temporal scales. Understanding the physical processes driving the strong variability is of fundamental importance for constraining the effect of marine emissions from upwelling regions on the global CO2 budget. In this study, a frontal decay on length scales of 𝒪(10 km) was observed off the Peruvian coast following a pronounced decrease in down-frontal (equatorward) wind speed with a time lag of 9 h. Simultaneously, the sea-to-air flux of CO2 on the inshore (cold) side of the front dropped from up to 80 to 10 mmol m−2 day−1, while the offshore (warm) side of the front was constantly outgassing at a rate of 10–20 mmol m−2 day−1. Based on repeated ship transects the decay of the front was observed to occur in two phases. The first phase was characterized by a development of coherent surface temperature anomalies which gained in amplitude over 6–9 h. The second phase was characterized by a disappearance of the surface temperature front within 6 h. Submesoscale mixed-layer instabilities were present but seem too slow to completely remove the temperature gradient in this short time period. Dynamics such as a pressure-driven gravity current appear to be a likely mechanism behind the evolution of the front.

Description: A major role in regulation of global methane fluxes has been attributed to the process of anaerobic oxidation of methane (AOM), which is performed by consortia of methanotrophic archaea and sulfate reducing bacteria. An important question remains how these energy limited, slow growing Microorganisms with generation times of 3–7 months respond to rapid natural variations in methane fluxes at cold seeps. We used an experimental flow-through column system filled with cold seep sediments naturally enriched in methanotrophic communities, to test their responses to short-term variations in methane and sulfate fluxes. At stable methane and sulfate concentrations of ∼2 mM and 28 mM, respectively, we measured constant rates of AOM and sulfate reduction (SR) for up to 160 days of incubation. When percolated with methane-free medium, the anaerobic methanotrophs ceased to produce sulfide. After a starvation phase of 40 days, the addition of methane restored former AOM and SR rates immediately. At methane concentrations between 0–2.3 mM we measured a linear correlation between methane availability, AOM and SR. At constant fluid flow velocities of 30 m yr−1, ca. 50% of the methane was consumed by the anaerobic methanotrophic (ANME) population at all concentrations tested. Reducing the sulfate concentration from 28 to 1 mM, a decrease in AOM and SR by 50% was observed, and 45% of the methane was consumed. Hence, the marine anaerobic methanotrophs(ANME) are capable of oxidizing substantial amounts of methane over a wide and variable range of fluxes of the reaction educts.

Description: The island of South Georgia is situated in the iron (Fe) depleted Antarctic Circumpolar Current of the Southern Ocean. Iron emanating from its shelf system fuels large phytoplankton blooms downstream of the island, but the actual supply mechanisms are unclear. To address this we present the first inventory of Fe, manganese (Mn) and aluminium (Al) in shelf sediments, pore waters and the water column in the vicinity of South Georgia, alongside data on zooplankton-mediated Fe cycling processes. The seafloor sediments were the main particulate Fe source to shelf bottom waters as indicated by Fe / Mn and Fe / Al ratios for shelf sediments and suspended particles in the water column. Less than 1 % of the total particulate Fe pool was leachable surface adsorbed (labile) Fe, and therefore potentially available to organisms. Pore waters formed the primary dissolved Fe (DFe) source to shelf bottom waters supplying 0.1–4 μmol DFe m−2 d−1. However, only 0.41 ± 0.26 μmol DFe m−2 d−1 was transferred to the surface mixed layer by vertical diffusive and advective mixing. Other trace metal sources to surface waters included glacial flour released by melting glaciers and zooplankton excretion processes. On average 6.5 ± 8.2 μmol m−2 d−1 of labile particulate Fe was supplied to the surface mixed layer via krill faecal pellets, with further DFe released by krill at around 1.1 ± 2.2 μmol m−2 d−1. The faecal pellets released by krill constituted of seafloor derived lithogenic material and settled algae debris, in addition to freshly ingested suspended phytoplankton specimen. The phytoplankton Fe requirement in the blooms ca. 1250 km downstream the island of South Georgia was 0.33 ± 0.11 μmol m−2 d−1, with the DFe supply by horizontal/vertical mixing, deep winter mixing and via aeolian dust estimated as ~ 0.12 μmol m−2 d−1. We suggest that additionally required DFe was provided through recycling of biogenically stored Fe following luxury Fe uptake by phytoplankton on the Fe rich shelf. This process would allow Fe to be retained in the surface mixed layer of waters downstream of South Georgia through continuous recycling and biological uptake, and facilitate the large scale blooms.

Description: In estuarine coastal systems such as the Baltic Sea, mussels suffer from low salinity which limits their distribution. Anthropogenic climate change is expected to cause further desalination which will lead to local extinctions of mussels in the low saline areas. It is commonly accepted that mussel distribution is limited by osmotic stress. However, along the salinity gradient environmental conditions for biomineralization are successively becoming more adverse as a result of reduced [Ca2+] and dissolved inorganic carbon (CT) availability. In larvae, calcification is an essential process starting during early development with formation of the prodissoconch I (PD I) shell which is completed under optimal conditions within 2 days. Experimental manipulations of seawater [Ca2+] start to impair PD I formation in Mytilus larvae at concentrations below 3 mM, which corresponds to conditions present in the Baltic at salinities below 8 g kg-1. In addition, lowering dissolved inorganic carbon to critical concentrations (〈 1 mM) similarly affected PD I size which was well correlated with calculated ΩAragonite and [Ca2+][HCO3-]/[H+] in all treatments. Comparing results for larvae from the western Baltic with a population from the central Baltic revealed significantly higher tolerance of PD I formation to lowered [Ca2+] and [Ca2+][HCO3-]/[H+] in the low saline adapted population. This may result from genetic adaptation to the more adverse environmental conditions prevailing in the low saline areas of the Baltic. The combined effects of lowered [Ca2+] and adverse carbonate chemistry represent major limiting factors for bivalve calcification and can thereby contribute to distribution limits of mussels in the Baltic Sea.

Description: The trace metal iron (Fe) is an essential micronutrient for phytoplankton growth and limits, or co-limits primary production across much of the world's surface ocean. Iron is a redox sensitive element, with Fe(II) and Fe(III) co-existing in natural waters. Whilst Fe(II) is the most soluble form, it is also transient with rapid oxidation rates in oxic seawater. Measurements of Fe(II) are therefore preferably undertaken in situ. For this purpose an autonomous wet chemical analyzer based on lab-on-chip technology was developed for the in situ determination of the concentration of dissolved (〈0.45 μm) Fe species (Fe(II) and labile Fe) suitable for deployments in a wide range of aquatic environments. The spectrophotometric approach utilizes a buffered ferrozine solution and a ferrozine/ascorbic acid mixture for Fe(II) and labile Fe(III) analyses, respectively. Diffusive mixing, color development and spectrophotometric detection take place in three separate flow cells with different lengths such that the analyzer can measure a broad concentration range from low nM to several μM of Fe, depending on the desired application. A detection limit of 1.9 nM Fe was found. The microfluidic analyzer was tested in situ for nine days in shallow waters in the Kiel Fjord (Germany) along with other sensors as a part of the SenseOCEAN EU-project. The analyzer's performance under natural conditions was assessed with discrete samples collected and processed according to GEOTRACES protocol [acidified to pH 〈 2 and analyzed via inductively coupled plasma mass spectrometry (ICP-MS)]. The mechanical performance of the analyzer over the nine day period was good (consistent high precision of Fe(II) and Fe(III) standards with a standard deviation of 2.7% (n = 214) and 1.9% (n = 217), respectively, and successful completion of every programmed data point). However, total dissolved Fe was consistently low compared to ICP-MS data. Recoveries between 16 and 75% were observed, indicating that the analyzer does not measure a significant fraction of natural dissolved Fe species in coastal seawater. It is suggested that an acidification step would be necessary in order to ensure that the analyzer derived total dissolved Fe concentration is reproducible and consistent with discrete values.

Description: Atmospheric deposition is a major source of trace metals in marine surface waters and supplies vital micronutrients to phytoplankton, yet measured aerosol trace metal solubility values are operationally defined, and there are relatively few multi-element studies on aerosol-metal solubility in seawater. Here we measure the solubility of aluminum (Al), cadmium (Cd), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn) from natural aerosol samples in seawater over a 7 days period to (1) evaluate the role of extraction time in trace metal dissolution behavior and (2) explore how the individual dissolution patterns could influence biota. Dissolution behavior occurs over a continuum ranging from rapid dissolution, in which the majority of soluble metal dissolved immediately upon seawater exposure (Cd and Co in our samples), to gradual dissolution, where metals dissolved slowly over time (Zn, Mn, Cu, and Al in our samples). Additionally, dissolution affected by interactions with particles was observed in which a decline in soluble metal concentration over time occurred (Fe and Pb in our samples). Natural variability in aerosol chemistry between samples can cause metals to display different dissolution kinetics in different samples, and this was particularly evident for Ni, for which samples showed a broad range of dissolution rates. The elemental molar ratio of metals in the bulk aerosols was 23,189Fe: 22,651Al: 445Mn: 348Zn: 71Cu: 48Ni: 23Pb: 9Co: 1Cd, whereas the seawater soluble molar ratio after 7 days of leaching was 11Fe: 620Al: 205Mn: 240Zn: 20Cu: 14Ni: 9Pb: 2Co: 1Cd. The different kinetics and ratios of aerosol metal dissolution have implications for phytoplankton nutrition, and highlight the need for unified extraction protocols that simulate aerosol metal dissolution in the surface ocean.

Description: Coastal California is a dynamic upwelling region where nitrogen (N) and iron (Fe) can both limit productivity and influence biogeochemistry over different spatial and temporal scales. With global change, the flux of nitrate from upwelling is expected to increase over the next century, potentially driving additional oceanic regions toward Fe limitation. In this study we explored the effect of changes in Fe/N ratio on native phytoplankton from five currently Fe-replete sites near the major California upwelling centers at Bodega Bay and Monterey Bay using nutrient addition incubation experiments. Despite the high nitrate levels (13–30 μ M) in the upwelled water, phytoplankton at three of the five sites showed increased growth when 10 μ M nitrate was added. None of the sites showed enhanced growth following addition of 10 nM Fe. Nitrate additions favored slow sinking single-celled diatoms over faster sinking chain-forming diatoms, suggesting that future increases in nitrate flux could affect carbon and silicate export and alter grazer populations. In particular, solitary cells of Cylindrotheca were more abundant than the toxin-producing genus Pseudonitzschia following nitrate addition. These responses suggest the biogeochemistry of coastal California could change in response to future increases in nitrate, and multiple stressors like ocean acidification and hypoxia may further result in ecosystem shifts.

Description: The response of the marine carbon cycle to changes in atmospheric CO2 concentrations will be determined, in part, by the relative response of calcifying and non-calcifying organisms to global change. Planktonic foraminifera are responsible for a quarter or more of global carbonate production, therefore understanding the sensitivity of calcification in these organisms to environmental change is critical. Despite this, there remains little consensus as to whether, or to what extent, chemical and physical factors affect foraminiferal calcification. To address this, we directly test the effect of multiple controls on calcification in culture experiments and core-top measurements of Globigerinoides ruber. We find that two factors, body size and the carbonate system, strongly influence calcification intensity in life, but that exposure to corrosive bottom waters can overprint this signal post mortem. Using a simple model for the addition of calcite through ontogeny, we show that variable body size between and within datasets could complicate studies that examine environmental controls on foraminiferal shell weight. In addition, we suggest that size could ultimately play a role in determining whether calcification will increase or decrease with acidification. Our models highlight that knowledge of the specific morphological and physiological mechanisms driving ontogenetic change in calcification in different species will be critical in predicting the response of foraminiferal calcification to future change in atmospheric pCO2.

Description: The distribution of dissolved aluminium (dAl) in the water column of the North Atlantic and Labrador Sea was studied along GEOTRACES section GA01 to unravel the sources and sinks of this element. Surface water dAl concentrations were low (median of 2.5 nM) due to low aerosol deposition and removal by phytoplankton. However, surface water dAl concentrations were enhanced on the Iberian and Greenland shelves (up to 30.9 nM) due to continental inputs (rivers, glacial flour and ice melt). A negative correlation was observed between dAl in surface waters and primary production, phytoplankton community structure and biogenic opal production. The abundance of diatoms exerted a significant (p 〈 0.01) control on the surface particulate Al (pAl) to dAl ratios by decreasing dAl levels and increasing pAl levels. Dissolved Al concentrations generally increased with depth and correlated strongly with silicate (R2 〉 0.76) west of the Iberian Basin, suggesting net release of dAl at depth during remineralization of sinking biogenic opal containing particles. Enrichment of dAl at near-bottom depths was observed due to resuspension of sediments near the sediment-water interface. The highest dAl (up to 38.7 nM) concentrations were observed in Mediterranean Overflow Waters which act as a major source of dAl to mid depth waters of the eastern North Atlantic. This study clearly shows that the vertical and lateral distribution of dAl in the North Atlantic differs when compared to other regions of the North Atlantic and global ocean due to the large spatial differences both in the main source of Al, atmospheric deposition, and the main sink for Al, particle scavenging, between different oceanic regions.

Description: The Rare Earth Elements (REEs) have been widely used to investigate marine biogeochemical processes as well as the sources and mixing of water masses. However, there are still important uncertainties about the global aqueous REE cycle with respect to the contributions of highly reactive basaltic minerals originating from volcanic islands and the role of Submarine Groundwater Discharge (SGD). Here we present dissolved REE concentrations obtained from waters at the island-ocean interface (including SGD, river, lagoon and coastal waters) from the island of Tahiti and from three detailed open ocean profiles on the Manihiki Plateau (including neodymium (Nd) isotope compositions), which are located in ocean currents downstream of Tahiti. Tahitian fresh waters have highly variable REE concentrations that likely result from variable water–rock interaction and removal by secondary minerals. In contrast to studies on other islands, the SGD samples do not exhibit elevated REE concentrations but have distinctive REE distributions and Y/Ho ratios. The basaltic Tahitian rocks impart a REE pattern to the waters characterized by a middle REE enrichment, with a peak at europium similar to groundwaters and coastal waters of other volcanic islands in the Pacific. However, the basaltic island REE characteristics (with the exception of elevated Y/Ho ratios) are lost during transport to the Manihiki Plateau within surface waters that also exhibit highly radiogenic Nd isotope signatures. Our new data demonstrate that REE concentrations are enriched in Tahitian coastal water, but without multidimensional sampling, basaltic island Nd flux estimates range over orders of magnitude from relatively small to globally significant. Antarctic Intermediate Water (AAIW) loses its characteristic Nd isotopic signature (-6 to-9) around the Manihiki Plateau as a consequence of mixing with South Equatorial Pacific Intermediate Water (SEqPIW), which shows more positive values (-1 to -2). However, an additional Nd input/exchange along the pathway of AAIW, eventually originating from the volcanic Society, Tuamotu and Tubuai Islands (including Tahiti), is indicated by an offset from the mixing array of AAIW and SEqPIW to more radiogenic Nd isotope compositions.

Description: Autonomous underwater vehicles (AUVs) offer unique possibilities for exploring the deep seafloor in high resolution over large areas. We highlight the results from AUV-based multibeam echosounder (MBES) bathymetry / backscatter and digital optical imagery from the DISCOL area acquired during research cruise SO242 in 2015. AUV bathymetry reveals a morphologically complex seafloor with rough terrain in seamount areas and low-relief variations in sedimentary abyssal plains which are covered in Mn-nodules. Backscatter provides valuable information about the seafloor type and particularly about the influence of Mn-nodules on the response of the transmitted acoustic signal. Primarily, Mn-nodule abundances were determined by means of automated nodule detection on AUV seafloor imagery and nodule metrics such as nodules m−2 were calculated automatically for each image allowing further spatial analysis within GIS in conjunction with the acoustic data. AUV-based backscatter was clustered using both raw data and corrected backscatter mosaics. In total, two unsupervised methods and one machine learning approach were utilized for backscatter classification and Mn-nodule predictive mapping. Bayesian statistical analysis was applied to the raw backscatter values resulting in six acoustic classes. In addition, Iterative Self-Organizing Data Analysis (ISODATA) clustering was applied to the backscatter mosaic and its statistics (mean, mode, 10th, and 90th quantiles) suggesting an optimum of six clusters as well. Part of the nodule metrics data was combined with bathymetry, bathymetric derivatives and backscatter statistics for predictive mapping of the Mn-nodule density using a Random Forest classifier. Results indicate that acoustic classes, predictions from Random Forest model and image-based nodule metrics show very similar spatial distribution patterns with acoustic classes hence capturing most of the fine-scale Mn-nodule variability. Backscatter classes reflect areas with homogeneous nodule density. A strong influence of mean backscatter, fine scale BPI and concavity of the bathymetry on nodule prediction is seen. These observations imply that nodule densities are generally affected by local micro-bathymetry in a way that is not yet fully understood. However, it can be concluded that the spatial occurrence of Mn-covered areas can be sufficiently analysed by means of acoustic classification and multivariate predictive mapping allowing to determine the spatial nodule density in a much more robust way than previously possible.

Description: The benthic environment is a crucial component of marine systems in the provision of ecosystem services, sustaining biodiversity and in climate regulation, and therefore important to human society. With the contemporary increase in computational power, model resolution and technological improvements in quality and quantity of benthic data, it is necessary to ensure that benthic systems are appropriately represented in coupled benthic-pelagic biogeochemical and ecological modelling studies. In this paper we focus on five topical challenges related to various aspects of modelling benthic environments: organic matter reactivity, dynamics of benthic-pelagic boundary layer, microphytobenthos, biological transport and small-scale heterogeneity, and impacts of episodic events. We discuss current gaps in their understanding and indicate plausible ways ahead. Further, we propose a three-pronged approach for the advancement of benthic and benthic-pelagic modelling, essential for improved understanding, management and prediction of the marine environment. This includes: (A) development of a traceable and hierarchical framework for benthic-pelagic models, which will facilitate integration among models, reduce risk of bias, and clarify model limitations; (B) extended cross-disciplinary approach to promote effective collaboration between modelling and empirical scientists of various backgrounds and better involvement of stakeholders and end-users; (C) a common vocabulary for terminology used in benthic modelling, to promote model development and integration, and also to enhance mutual understanding.

Description: Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere – the "global carbon budget" – 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 methodology to quantify the five major components of the global carbon budget and their uncertainties. CO2 emissions from fossil fuels and industry (EFF) are based on energy statistics and cement production data, respectively, while emissions from land-use change (ELUC), mainly deforestation, are based on land-cover change data and bookkeeping models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The ocean CO2 sink (SOCEAN) and terrestrial CO2 sink (SLAND) are estimated with global process models constrained by observations. The resulting carbon budget imbalance (BIM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of imperfect data and understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the last decade available (2007–2016), EFF was 9.4 ± 0.5 GtC yr−1, ELUC 1.3 ± 0.7 GtC yr−1, GATM 4.7 ± 0.1 GtC yr−1, SOCEAN 2.4 ± 0.5 GtC yr−1, and SLAND 3.0 ± 0.8 GtC yr−1, with a budget imbalance BIM of 0.6 GtC yr−1 indicating overestimated emissions and/or underestimated sinks. For year 2016 alone, the growth in EFF was approximately zero and emissions remained at 9.9 ± 0.5 GtC yr−1. Also for 2016, ELUC was 1.3 ± 0.7 GtC yr−1, GATM was 6.1 ± 0.2 GtC yr−1, SOCEAN was 2.6 ± 0.5 GtC yr−1, and SLAND was 2.7 ± 1.0 GtC yr−1, with a small BIM of −0.3 GtC. GATM continued to be higher in 2016 compared to the past decade (2007–2016), reflecting in part the high fossil emissions and the small SLAND consistent with El Niño conditions. The global atmospheric CO2 concentration reached 402.8 ± 0.1 ppm averaged over 2016. For 2017, preliminary data for the first 6–9 months indicate a renewed growth in EFF of +2.0 % (range of 0.8 to 3.0 %) based on national emissions projections for China, USA, and India, and projections of gross domestic product (GDP) corrected for recent changes in the carbon intensity of the economy for the rest of the world. This living data update documents changes in the methods and data sets used in this new global carbon budget compared with previous publications of this data set (Le Quéré et al., 2016, 2015b, a, 2014, 2013). All results presented here can be downloaded from https://doi.org/10.18160/GCP-2017 (GCP, 2017).

Description: In the surface ocean, microorganisms are both a source of extracellular H2O2 and, via the production of H2O2 destroying enzymes, also one of the main H2O2 sinks. Within microbial communities, H2O2 sources and sinks may be unevenly distributed and thus microbial community structure could influence ambient extracellular H2O2 concentrations. Yet the biogeochemical cycling of H2O2 and other reactive oxygen species (ROS) is rarely investigated at the community level. Here, we present a time series of H2O2 concentrations during a 28-day mesocosm experiment where a pCO2 gradient (400–1,450 μatm) was applied to subtropical North Atlantic waters. Pronounced changes in H2O2 concentration were observed over the duration of the experiment. Initially H2O2 concentrations in all mesocosms were strongly correlated with surface H2O2 concentrations in ambient seawaters outside the mesocosms which ranged from 20 to 92 nM over the experiment duration (Spearman Rank Coefficients 0.79–0.93, p-values 〈 0.001–0.015). After approximately 9 days of incubation however, H2O2 concentrations had increased across all mesocosms, later reaching 〉300 nM in some mesocosms (2–6 fold higher than ambient seawaters). The correlation with ambient H2O2 was then no longer significant (p 〉 0.05) in all treatments. Furthermore, changes in H2O2 could not be correlated with inter-day changes in integrated irradiance. Yet H2O2 concentrations in most mesocosms were inversely correlated with bacterial abundance (negative Spearman Rank Coefficients ranging 0.59–0.94, p-values 〈 0.001–0.03). Our results therefore suggest that ambient H2O2 concentration can be influenced by microbial community structure with shifts toward high bacterial abundance correlated with low extracellular H2O2 concentrations. We also infer that the nature of mesocosm experiment design, i.e., the enclosure of water within open containers at the ocean surface, can strongly influence extracellular H2O2 concentrations. This has potential chemical and biological implications during incubation experiments due to the role of H2O2 as both a stressor to microbial functioning and a reactive component involved in the cycling of numerous chemical species including, for example, trace metals and haloalkanes.

Description: We have assessed how varying CO2 (180, 380, and 720 μatm) and growth light intensity (40 and 400 μmol photons m−2 s−1) affected Trichodesmium erythraeum IMS101 growth and photophysiology over free iron (Fe′) concentrations between 20 and 9,600 pM. We found significant iron dependencies of growth rate and the initial slope and maximal relative PSII electron transport rates (rPm). Under iron-limiting concentrations, high-light increased growth rates and rPm; possibly indicating a lower allocation of resources to iron-containing photosynthetic proteins. Higher CO2 increased growth rates across all iron concentrations, enabled growth to occur at lower Fe′ concentrations, increased rPm and lowered the iron half saturation constants for growth (Km). We attribute these CO2 responses to the operation of the CCM and the ATP spent/saved for CO2 uptake and transport at low and high CO2, respectively. It seems reasonable to conclude that T. erythraeum IMS101 can exhibit a high degree of phenotypic plasticity in response to CO2, light intensity and iron-limitation. These results are important given predictions of increased dissolved CO2 and water column stratification (i.e., higher light exposures) over the coming decades.