ALBERT

Description: Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I). The input of marine halogens to the stratosphere is based on observations and modeling studies using low resolution oceanic emission scenarios derived from top down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1° × 1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr−1 for CHBr3, 0.78/0.98 Gmol Br yr−1 for CH2Br2 and 1.24/1.45 Gmol I yr−1 for CH3I (Robust Fit/Ordinary Least Square regression technique). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic region. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An underrepresentation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom up emission estimate and top down approaches

Description: The volume of water enclosed inside flexible-wall mesocosm bags is hard to estimate using geometrical calculations and can be strongly variable among bags of the same dimensions. Here we present a method for precise water volume determination in mesocosms using salinity as a tracer. Knowledge of the precise volume of water enclosed allows establishment of exactly planed treatment concentrations and calculation of elemental budgets.

Description: The increase in atmospheric carbon dioxide (CO2) results in acidification of the oceans, expected to lead to the fastest drop in ocean pH in the last 300 million years, if anthropogenic emissions are continued at present rate. Due to higher solubility of gases in cold waters and increased exposure to the atmosphere by decreasing ice cover, the Arctic Ocean will be among the areas most strongly affected by ocean acidification. Yet, the response of the plankton community of high latitudes to ocean acidification has not been studied so far. This work is part of the Arctic campaign of the European Project on Ocean Acidification (EPOCA) in 2010, employing 9 in situ mesocosms of about 45 000 l each to simulate ocean acidification in Kongsfjorden, Svalbard (78°56.2' N 11°53.6' E). In the present study, we investigated effects of elevated CO2 on the composition and richness of particle attached (PA; 〉3 μm) and free living (FL; 〈3 μm 〉0.2 μm) bacterial communities by Automated Ribosomal Intergenic Spacer Analysis (ARISA) in 6 of the mesocosms and the surrounding fjord, ranging from 185 to 1050 initial μatm pCO2. ARISA was able to resolve about 20–30 bacterial band-classes per sample and allowed for a detailed investigation of the explicit richness. Both, the PA and the FL bacterioplankton community exhibited a strong temporal development, which was driven mainly by temperature and phytoplankton development. In response to the breakdown of a picophytoplankton bloom (phase 3 of the experiment), number of ARISA-band classes in the PA-community were reduced at low and medium CO2 (∼180–600 μatm) by about 25%, while it was more or less stable at high CO2 (∼ 650–800 μatm). We hypothesise that enhanced viral lysis and enhanced availability of organic substrates at high CO2 resulted in a more diverse PA-bacterial community in the post-bloom phase. Despite lower cell numbers and extracellular enzyme activities in the post-bloom phase, bacterial protein production was enhanced in high CO2-treatments, suggesting a positive effect of community richness on this function and on carbon cycling by bacteria.

Description: One of the great challenges in ocean change research is to understand and forecast the effects of environmental changes on pelagic communities and the associated impacts on biogeochemical cycling. Mesocosms, experimental enclosures designed to approximate natural conditions, and in which environmental factors can be manipulated and closely monitored, provide a powerful tool to close the gap between single species laboratory experiments and observational and correlative approaches applied in field surveys. Existing pelagic mesocosm systems are stationary and/or restricted to well-protected waters. To allow mesocosm experimentation in a range of hydrographic conditions and in areas considered most sensitive to ocean change, we developed a mobile, sea-going mesocosm facility, the Kiel Off-Shore Mesocosms for Future Ocean Simulations (KOSMOS). The KOSMOS platform, which can be transported and deployed by mid-sized research vessels, is designed for operation in moored and free-floating mode under low to moderate wave conditions (up to 2.5 m wave heights). It encloses a water column 2 m in diameter and 15 to 25 m deep (~50–75 m3 in volume) without disrupting the vertical structure or disturbing the enclosed plankton community. Several new developments in mesocosm design and operation were implemented to (i) minimize differences in starting conditions between mesocosms, (ii) allow for extended experimental duration, (iii) precisely determine the mesocosm volume, (iv) determine air–sea gas exchange, and (v) perform mass balance calculations. After multiple test runs in the Baltic Sea, which resulted in continuous improvement of the design and handling, the KOSMOS platform successfully completed its first full-scale experiment in the high Arctic off Svalbard (78° 56.2′ N, 11° 53.6′ E) in June/July 2010. The study, which was conducted in the framework of the European Project on Ocean Acidification (EPOCA), focused on the effects of ocean acidification on a natural plankton community and its impacts on biogeochemical cycling and air/sea exchange of climate relevant gases. This manuscript describes the mesocosm hardware, its deployment and handling, CO2 manipulation, sampling and cleaning, including some further modifications conducted based on the experiences gained during this study.

Description: Ocean acidification and carbonation, driven by anthropogenic emissions of carbon dioxide (CO2), have been shown to affect a variety of marine organisms and are likely to change ecosystem functioning. High latitudes, especially the Arctic, will be the first to encounter profound changes in carbonate chemistry speciation at a large scale, namely the under-saturation of surface waters with respect to aragonite, a calcium carbonate polymorph produced by several organisms in this region. During a CO2 perturbation study in 2010, in the framework of the EU-funded project EPOCA, the temporal dynamics of a plankton bloom was followed in nine mesocosms, manipulated for CO2 levels ranging initially from about 185 to 1420 μatm. Dissolved inorganic nutrients were added halfway through the experiment. Autotrophic biomass, as identified by chlorophyll a standing stocks (Chl a), peaked three times in all mesocosms. However, while absolute Chl a concentrations were similar in all mesocosms during the first phase of the experiment, higher autotrophic biomass was measured at high in comparison to low CO2 during the second phase, right after dissolved inorganic nutrient addition. This trend then reversed in the third phase. There were several statistically significant CO2 effects on a variety of parameters measured in certain phases, such as nutrient utilization, standing stocks of particulate organic matter, and phytoplankton species composition. Interestingly, CO2 effects developed slowly but steadily, becoming more and more statistically significant with time. The observed CO2 related shifts in nutrient flow into different phytoplankton groups (mainly diatoms, dinoflagellates, prasinophytes and haptophytes) could have consequences for future organic matter flow to higher trophic levels and export production, with consequences for ecosystem productivity and atmospheric CO2.

Description: The deposition of atmospheric dust is the primary process supplying trace elements abundant in crustal rocks (e.g. Al, Mn and Fe) to the surface ocean. Upon deposition, the residence time in surface waters for each of these elements differs according to their chemical speciation and biological utilization. Presently, however, the chemical and physical processes occurring after atmospheric deposition are poorly constrained, principally because of the difficulty in following natural dust events in situ. In the present work we examined the temporal changes in the biogeochemistry of crustal metals (in particular Al, Mn and Fe) after an artificial dust deposition event. The experiment was contained inside trace metal clean mesocosms (0–12.5 m depths) deployed in the surface waters of the northwestern Mediterranean, close to the coast of Corsica within the frame of the DUNE project (a DUst experiment in a low Nutrient, low chlorophyll Ecosystem). Two consecutive artificial dust deposition events, each mimicking a wet deposition of 10 g m−2 of dust, were performed during the course of this DUNE-2 experiment. The changes in dissolved manganese (Mn), iron (Fe) and aluminum (Al) concentrations were followed immediately after the seeding with dust and over the following week. The Mn, Fe and Al inventories and loss or dissolution rates were determined. The evolution of the inventories after the two consecutive additions of dust showed distinct behaviors for dissolved Mn, Al and Fe. Even though the mixing conditions differed from one seeding to the other, Mn and Al showed clear increases directly after both seedings due to dissolution processes. Three days after the dust additions, Al concentrations decreased as a consequence of scavenging on sinking particles. Al appeared to be highly affected by the concentrations of biogenic particles, with an order of magnitude difference in its loss rates related to the increase of biomass after the addition of dust. In the case of dissolved Fe, it appears that the first dust addition resulted in a decrease as it was scavenged by sinking dust particles, whereas the second seeding induced dissolution of Fe from the dust particles due to the excess Fe binding ligand concentrations present at that time. This difference, which might be related to a change in Fe binding ligand concentration in the mesocosms, highlights the complex processes that control the solubility of Fe. Based on the inventories at the mesocosm scale, the estimations of the fractional solubility of metals from dust particles in seawater were 1.44 ± 0.19% and 0.91 ± 0.83% for Al and 41 ± 9% and 27 ± 19% for Mn for the first and the second dust addition. These values are in good agreement with laboratory-based estimates. For Fe no fractional solubility was obtained after the first seeding, but 0.12 ± 0.03% was estimated after the second seeding. Overall, the trace metal dataset presented here makes a significant contribution to enhancing our knowledge on the processes influencing trace metal release from Saharan dust and the subsequent processes of bio-uptake and scavenging in a low nutrient, low chlorophyll area

Description: Sea surface and atmospheric measurements of dimethylsulphide (DMS) were performed during the TransBrom cruise in the western Pacific Ocean between Japan and Australia in October 2009. Air–sea DMS fluxes were computed between 0 and 30 μmol m−2 d−1, which are in agreement with those computed by the current climatology, and peak emissions of marine DMS into the atmosphere were found during the occurrence of tropical storm systems. Atmospheric variability in DMS, however, did not follow that of the computed fluxes and was more related to atmospheric transport processes. The computed emissions were used as input fields for the Lagrangian dispersion model FLEXPART, which was set up with actual meteorological fields from ERA-Interim data and different chemical lifetimes of DMS. A comparison with aircraft in situ data from the adjacent HIPPO2 campaign revealed an overall good agreement between modelled versus observed DMS profiles over the tropical western Pacific Ocean. Based on observed DMS emissions and meteorological fields along the cruise track, the model projected that up to 30 g S per month in the form of DMS, emitted from an area of 6 × 104 m2, can be transported above 17 km. This surprisingly large DMS entrainment into the stratosphere is disproportionate to the regional extent of the area of emissions and mainly due to the high convective activity in this region as simulated by the transport model. Thus, if DMS can cross the tropical tropopause layer (TTL), we suggest that the considerably larger area of the tropical western Pacific Ocean can be a source of sulphur to the stratosphere, which has not been considered as yet.

Description: This special section of Atmospheric Chemistry and Physics gives an overview of scientific results, collected during a West Pacific ship expedition in October 2009 with the Research Vessel (R/V) Sonne. The cruise focussed on chemical interactions between the ocean surface and the atmosphere above the tropical West Pacific and was planned within the national research project TransBrom (www.geomar.de/~transbrom). TransBrom aimed to particularly investigate very short lived bromine compounds in the ocean and their transport to and relevance for the stratosphere. For this purpose, chemical and biological parameters were analysed in the ocean and in the atmosphere, accompanied by a high frequency of meteorological measurements, to derive new insights into the multidisciplinary research field. This introduction paper presents the scientific goals and the meteorological and oceanographic background. The main research findings of the TransBrom Sonne expedition are highlighted.

Description: The effect of ocean acidification on the fatty acid composition of a natural plankton community in the Arctic was studied in a large-scale mesocosm experiment, carried out in Kongsfjorden (Svalbard, Norway) at 79° N. Nine mesocosms of ~50 m3 each were exposed to 8 different pCO2 levels (from natural background conditions to ~1420 μatm), yielding pH values (on the total scale) from ~8.3 to 7.5. Inorganic nutrients were added on day 13. The phytoplankton development during this 30-day experiment passed three distinct phases: (1) prior to the addition of inorganic nutrients, (2) first bloom after nutrient addition, and (3) second bloom after nutrient addition. The fatty acid composition of the natural plankton community was analysed and showed, in general, high percentages of polyunsaturated fatty acids (PUFAs): 44–60% of total fatty acids. Positive correlations with pCO2 were found for most PUFAs during phases 2 and/or 3, with the exception of 20:5n3 (eicosapentaenoic acid, EPA), an important diatom marker. These correlations are probably linked to changes in taxonomic composition in response to pCO2. While diatoms (together with prasinophytes and haptophytes) increased during phase 3 mainly in the low and intermediate pCO2 treatments, dinoflagellates were favoured by high CO2 concentrations during the same time period. This is reflected in the development of group-specific fatty acid trophic markers. No indications were found for a generally detrimental effect of ocean acidification on the planktonic food quality in terms of essential fatty acids.

Description: As a response to public demand for a well-documented, quality controlled, publically available, global surface ocean carbon dioxide (CO2) data set, the international marine carbon science community developed the Surface Ocean CO2 Atlas (SOCAT). The first SOCAT product is a collection of 6.3 million quality controlled surface CO2 data from the global oceans and coastal seas, spanning four decades (1968–2007). The SOCAT gridded data presented here is the second data product to come from the SOCAT project. Recognizing that some groups may have trouble working with millions of measurements, the SOCAT gridded product was generated to provide a robust, regularly spaced CO2 fugacity (fCO2) product with minimal spatial and temporal interpolation, which should be easier to work with for many applications. Gridded SOCAT is rich with information that has not been fully explored yet (e.g., regional differences in the seasonal cycles), but also contains biases and limitations that the user needs to recognize and address (e.g., local influences on values in some coastal regions).

Description: A well documented, publicly available, global data set of surface ocean carbon dioxide (CO2) parameters has been called for by international groups for nearly two decades. The Surface Ocean CO2 Atlas (SOCAT) project was initiated by the international marine carbon science community in 2007 with the aim of providing a comprehensive, publicly available, regularly updated, global data set of marine surface CO2, which had been subject to quality control (QC). Many additional CO2 data, not yet made public via the Carbon Dioxide Information Analysis Center (CDIAC), were retrieved from data originators, public websites and other data centres. All data were put in a uniform format following a strict protocol. Quality control was carried out according to clearly defined criteria. Regional specialists performed the quality control, using state-of-the-art web-based tools, specially developed for accomplishing this global team effort. SOCAT version 1.5 was made public in September 2011 and holds 6.3 million quality controlled surface CO2 data points from the global oceans and coastal seas, spanning four decades (1968–2007). Three types of data products are available: individual cruise files, a merged complete data set and gridded products. With the rapid expansion of marine CO2 data collection and the importance of quantifying net global oceanic CO2 uptake and its changes, sustained data synthesis and data access are priorities

Description: This study presents benthic data from 12 samplings from February to December 2010 in a 28 m deep channel in the southwest Baltic Sea. In winter, the distribution of solutes in the porewater was strongly modulated by bioirrigation which efficiently flushed the upper 10 cm of sediment, leading to concentrations which varied little from bottom water values. Solute pumping by bioirrigation fell sharply in the summer as the bottom waters became severely hypoxic (〈 2 μM O2). At this point the giant sulfide-oxidizing bacteria Beggiatoa was visible on surface sediments. Despite an increase in O2 following mixing of the water column in November, macrofauna remained absent until the end of the sampling. Contrary to expectations, metabolites such as dissolved inorganic carbon, ammonium and hydrogen sulfide did not accumulate in the upper 10 cm during the hypoxic period when bioirrigation was absent, but instead tended toward bottom water values. This was taken as evidence for episodic bubbling of methane gas out of the sediment acting as an abiogenic irrigation process. Porewater–seawater mixing by escaping bubbles provides a pathway for enhanced nutrient release to the bottom water and may exacerbate the feedback with hypoxia. Subsurface dissolved phosphate (TPO4) peaks in excess of 400 μM developed in autumn, resulting in a very large diffusive TPO4 flux to the water column of 0.7 ± 0.2 mmol m−2 d−1. The model was not able to simulate this TPO4 source as release of iron-bound P (Fe–P) or organic P. As an alternative hypothesis, the TPO4 peak was reproduced using new kinetic expressions that allow Beggiatoa to take up porewater TPO4 and accumulate an intracellular P pool during periods with oxic bottom waters. TPO4 is then released during hypoxia, as previous published results with sulfide-oxidizing bacteria indicate. The TPO4 added to the porewater over the year by organic P and Fe–P is recycled through Beggiatoa, meaning that no additional source of TPO4 is needed to explain the TPO4 peak. Further experimental studies are needed to strengthen this conclusion and rule out Fe–P and organic P as candidate sources of ephemeral TPO4 release. A measured C/P ratio of 〈 20 for the diffusive flux to the water column during hypoxia directly demonstrates preferential release of P relative to C under oxygen-deficient bottom waters. This coincides with a strong decrease in dissolved inorganic N/P ratios in the water column to ~ 1. Our results suggest that sulfide oxidizing bacteria could act as phosphorus capacitors in systems with oscillating redox conditions, releasing massive amounts of TPO4 in a short space of time and dramatically increasing the internal loading of TPO4 to the overlying water.

Description: The last interglaciation (~130 to 116 ka) is a time period with a strong astronomically induced seasonal forcing of insolation compared to the present. Proxy records indicate a significantly different climate to that of the modern, in particular Arctic summer warming and higher eustatic sea level. Because the forcings are relatively well constrained, it provides an opportunity to test numerical models which are used for future climate prediction. In this paper we compile a set of climate model simulations of the early last interglaciation (130 to 125 ka), encompassing a range of model complexities. We compare the simulations to each other and to a recently published compilation of last interglacial temperature estimates. We show that the annual mean response of the models is rather small, with no clear signal in many regions. However, the seasonal response is more robust, and there is significant agreement amongst models as to the regions of warming vs cooling. However, the quantitative agreement of the model simulations with data is poor, with the models in general underestimating the magnitude of response seen in the proxies. Taking possible seasonal biases in the proxies into account improves the agreement, but only marginally. However, a lack of uncertainty estimates in the data does not allow us to draw firm conclusions. Instead, this paper points to several ways in which both modelling and data could be improved, to allow a more robust model–data comparison.

Description: Sediment transport dynamics were studied during ice-free conditions under different atmospheric circulation regimes on the Laptev Sea shelf (Siberian Arctic). To study the interannual variability of suspended particulate matter (SPM) dynamics and their coupling with the variability in surface river water distribution on the Laptev Sea shelf, detailed oceanographic, optical (turbidity and Ocean Color satellite data), and hydrochemical (nutrients, SPM, stable oxygen isotopes) process studies were carried out continuously during the summers of 2007 and 2008. Thus, for the first time SPM and nutrient variations on the Laptev Sea shelf under different atmospheric forcing and the implications for the turbidity and transparency of the water column can be presented. The data indicate a clear link between different surface distributions of riverine waters and the SPM transport dynamics within the entire water column. The summer of 2007 was dominated by shoreward winds and an eastward transport of riverine surface waters. The surface SPM concentration on the southeastern inner shelf was elevated, which led to decreased transmissivity and increased light absorption. Surface SPM concentrations in the central and northern Laptev Sea were comparatively low. However, the SPM transport and concentration within the bottom nepheloid layer increased considerably on the entire eastern shelf. The summer of 2008 was dominated by offshore winds and northward transport of the river plume. The surface SPM transport was enhanced and extended onto the mid-shelf, whereas the bottom SPM transport and concentration was diminished. This study suggests that the SPM concentration and transport, in both the surface and bottom nepheloid layers, are associated with the distribution of riverine surface waters which are linked to the atmospheric circulation patterns over the Laptev Sea and the adjacent Arctic Ocean during the open water season. A continuing trend toward shoreward winds, weaker stratification and higher SPM concentration throughout the water column might have severe consequences for the ecosystem on the Laptev Sea shelf.

Description: Here we present results of the first comprehensive study of sulphur compounds and methane in the oligotrophic tropical West Pacific Ocean. The concentrations of dimethylsuphide (DMS), dimethylsulphoniopropionate (DMSP), dimethylsulphoxide (DMSO), and methane (CH4), as well as various phytoplankton marker pigments in the surface ocean were measured along a north-south transit from Japan to Australia in October 2009. DMS (0.9 nmol l−1), dissolved DMSP (DMSPd, 1.6 nmol l−1) and particulate DMSP (DMSPp, 2 nmol l−1) concentrations were generally low, while dissolved DMSO (DMSOd, 4.4 nmol l−1) and particulate DMSO (DMSOp, 11.5 nmol l−1) concentrations were comparably enhanced. Positive correlations were found between DMSO and DMSP as well as DMSP and DMSO with chlorophyll a, which suggests a similar source for both compounds. Similar phytoplankton groups were identified as being important for the DMSO and DMSP pool, thus, the same algae taxa might produce both DMSP and DMSO. In contrast, phytoplankton seemed to play only a minor role for the DMS distribution in the western Pacific Ocean. The observed DMSPp : DMSOp ratios were very low and seem to be characteristic of oligotrophic tropical waters representing the extreme endpoint of the global DMSPp : DMSOp ratio vs. SST relationship. It is most likely that nutrient limitation and oxidative stress in the tropical West Pacific Ocean triggered enhanced DMSO production leading to an accumulation of DMSO in the sea surface. Positive correlations between DMSPd and CH4, as well as between DMSO (particulate and total) and CH4, were found along the transit. We conclude that both DMSP and DMSO serve as substrates for methanogenic bacteria in the western Pacific Ocean.

Description: The effect of CO2 on carbon fluxes in Arctic plankton communities was investigated during the 2010 EPOCA mesocosm study in Ny Ålesund, Svalbard. Nine mesocosms were set up with initial pCO2 levels ranging from 185 to 1420 μatm for 5 weeks. 13C labelled bicarbonate was added at the start of the experiment to follow the transfer of carbon from dissolved inorganic carbon (DIC) into phytoplankton, bacteria, total particulate organic carbon (POC), zooplankton, and settling particles. Polar lipid derived fatty acids (PLFA) were used to trace carbon dynamics of phytoplankton and bacteria and allowed distinction of two groups of phytoplankton: phyto I (autotrophs) and phyto II (mixotrophs). Nutrients were added on day 13. A nutrient-phytoplankton-zooplankton-detritus model amended with 13C dynamics was constructed and fitted to the data to quantify uptake rates and carbon fluxes in the plankton community during the phase prior to nutrient addition (phase 1, days 0–12). During the first 12 days, a phytoplankton bloom developed that was characterized by high growth rates (0.87 days−1) for phyto I and lower growth rates (0.18 days−1) for phyto II. A large part of the carbon fixed by phytoplankton (~31%) was transferred to bacteria, while mesozooplankton grazed only ~6% of the production. After 6 days, the bloom collapsed and part of the organic matter subsequently settled into the sediment traps. The sedimentation losses of detritus in phase 1 were low (0.008 days−1) and overall export was only ~7% of production. Zooplankton grazing and detritus sinking losses prior to nutrient addition were sensitive to CO2: grazing decreased with increasing CO2, while sinking increased. Phytoplankton production increased again after nutrient addition on day 13. Although phyto II showed initially higher growth rates with increasing CO2 (days 14–22), the overall production of POC after nutrient addition (phase 2, days 14–29) decreased with increasing CO2. Significant sedimentation occurred towards the end of the experiment (after day 24) and much more material settled down in the sediment traps at low CO2.

Description: Diazotrophic cyanobacteria often form extensive summer blooms in the Baltic Sea driving their environment into phosphate limitation. One of the main species is the heterocystous cyanobacterium Nodularia spumigena. N. spumigena exhibits accelerated uptake of phosphate through the release of the exoenzyme alkaline phosphatase that also serves as an indicator of the hydrolysis of dissolved organic phosphorus (DOP). The present study investigated the utilization of DOP and its compounds (e.g. ATP) by N. spumigena during growth under varying CO2 concentrations, in order to estimate potential consequences of ocean acidification on the cell's supply with phosphorus. Cell growth, phosphorus pool fractions, and four DOP-compounds (ATP, DNA, RNA, and phospholipids) were determined in three set-ups with different CO2 concentrations (341, 399, and 508 μatm) during a 15-day batch experiment. The results showed rapid depletion of dissolved inorganic phosphorus (DIP) in all pCO2 treatments while DOP utilization increased with elevated pCO2, in parallel with the growth stimulation of N. spumigena. During the growth phase, DOP uptake was enhanced by a factor of 1.32 at 399 μatm and of 2.25 at 508 μatm compared to the lowest pCO2 concentration. Among the measured DOP compounds, none was found to accumulate preferentially during the incubation or in response to a specific pCO2 treatment. However, at the beginning 61.9 ± 4.3% of the DOP were not characterized but comprised the most highly utilized fraction. This is demonstrated by the decrement of this fraction to 27.4 ± 9.9% of total DOP during the growth phase, especially in response to the medium and high pCO2 treatment. Our results indicate a stimulated growth of diazotrophic cyanobacteria at increasing CO2 concentrations that is accompanied by increasing utilization of DOP as an alternative P source.

Description: Net community production (NCP) and carbon to nutrient uptake ratios were studied during a large-scale mesocosm experiment on ocean acidification in Kongsfjorden, western Svalbard, during June–July 2010. Nutrient depleted fjord water with natural plankton assemblages, enclosed in nine mesocosms of ~ 50 m3 in volume, was exposed to pCO2 levels ranging initially from 185 to 1420 μatm. NCP estimations are the cumulative change in dissolved inorganic carbon concentrations after accounting for gas exchange and total alkalinity variations. Stoichiometric coupling between inorganic carbon and nutrient net uptake is shown as a ratio of NCP to a cumulative change in inorganic nutrients. Phytoplankton growth was stimulated by nutrient addition half way through the experiment and three distinct peaks in chlorophyll a concentration were observed during the experiment. Accordingly, the experiment was divided in three phases. Cumulative NCP was similar in all mesocosms over the duration of the experiment. However, in phases I and II, NCP was higher and in phase III lower at elevated pCO2. Due to relatively low inorganic nutrient concentration in phase I, C : N and C : P uptake ratios were calculated only for the period after nutrient addition (phase II and phase III). For the total post-nutrient period (phase II + phase III) ratios were close to Redfield, however they were lower in phase II and higher in phase III. Variability of NCP, C : N and C : P uptake ratios in different phases reflects the effect of increasing CO2 on phytoplankton community composition and succession. The phytoplankton community was composed predominantly of haptophytes in phase I, prasinophytes, dinoflagellates, and cryptophytes in phase II, and haptophytes, prasinophytes, dinoflagellates and chlorophytes in phase III (Schulz et al., 2013). Increasing ambient inorganic carbon concentrations have also been shown to promote primary production and carbon assimilation. For this study, it is clear that the pelagic ecosystem response to increasing CO2 is more complex than that represented in previous work, e.g. Bellerby et al. (2008). Carbon and nutrient uptake representation in models should, where possible, be more focused on individual plankton functional types as applying a single stoichiometry to a biogeochemical model with regard to the effect of increasing pCO2 may not always be optimal. The phase variability in NCP and stoichiometry may be better understood if CO2 sensitivities of the plankton's functional type biogeochemical uptake kinetics and trophic interactions are better constrained.

Description: Increasing atmospheric CO2 is decreasing ocean pH most rapidly in colder regions such as the Arctic. As a component of the EPOCA pelagic mesocosm experiment off Spitzbergen in 2010, we examined the consequences of decreased pH and increased pCO2 on the concentrations of dimethylsulphide (DMS). DMS is an important reactant and contributor to aerosol formation and growth in the Arctic troposphere. In the nine mesocosms with initial pH 8.3 to 7.5, equivalent to pCO2 of 180 to 1420 μatm, highly significant but inverse responses to acidity (hydrogen ion concentration [H+]) occurred following nutrient addition. Compared to ambient [H+], average concentrations of DMS during the most representative phase of the 30 d experiment were reduced by approximately 60% at the highest [H+] and by 35% at [H+] equivalent to 750 μatm pCO2, as predicted for 2100. In contrast, concentrations of dimethylsulphoniopropionate (DMSP), the precursor of DMS, were elevated by approximately 50% at the highest [H+] and by 30% at [H+] corresponding to 750 μatm pCO2. Measurements of the specific rate of synthesis of DMSP by phytoplankton indicate increased production at high [H+], in parallel to rates of inorganic carbon fixation. The elevated DMSP production at high [H+] was largely a consequence of increased dinoflagellate biomass and in particular, the increased abundance of the species Heterocapsa rotundata. We discuss both phytoplankton and bacterial processes that may explain the reduced ratios of DMS:DMSPt at higher [H+]. The experimental design of eight treatment levels provides comparatively robust empirical relationships of DMS and DMSP concentration, DMSP production and dinoflagellate biomass versus [H+] in Arctic waters.

Description: Impacts of ocean acidification (OA) on marine biota have been observed in a wide range of marine systems. We used a mesocosm approach to study the response of a high Arctic coastal protozooplankton (PZP in the following) community during the post-bloom period in the Kongsfjorden (Svalbard) to direct and indirect effects of high pCO2/low pH. We found almost no direct effects of OA on PZP composition and diversity. Both, the relative shares of ciliates and heterotrophic dinoflagellates as well as the taxonomic composition of protozoans remained unaffected by changes in pCO2/pH. The different pCO2 treatments did not have any effect on food availability and phytoplankton composition and thus no indirect effects e.g. on the total carrying capacity and phenology of PZP could be observed. Our data points at a high tolerance of this Arctic PZP community to changes in pCO2/pH. Future studies on the impact of OA on plankton communities should include PZP in order to test whether the observed low sensitivity of protozoans to OA is typical for coastal communities where changes in seawater pH occur frequently.

Description: The marine nitrogen (N) inventory is controlled by the interplay of nitrogen loss processes, here referred to as denitrification, and nitrogen source processes, primarily nitrogen fixation. The apparent stability of the marine N inventory on time scales longer than the estimated N residence time, suggests some intimate balance between N sinks and sources. Such a balance may be perceived easier to achieve when N sinks and sources occur in close spatial proximity, and some studies have interpreted observational evidence for such a proximity as indication for a stabilizing feedback processes. Using a biogeochemical ocean circulation model, we here show instead that a close spatial association of N2 fixation and denitrification can, in fact, trigger destabilizing feedbacks on the N inventory and, because of stoichiometric constrains, lead to net N losses. Contrary to current notion, a balanced N inventory requires a regional separation of N sources and sinks. This can be brought about by factors that reduce the growth of diazotrophs, such as iron, or by factors that affect the fate of the fixed nitrogen remineralization, such as dissolved organic matter dynamics. In light of our findings we suggest that spatial arrangements of N sinks and sources have to be accounted for in addition to individual rate estimates for reconstructing past, evaluating present and predicting future marine N inventory imbalances.

Description: Decadal-to-century scale trends for a range of marine environmental variables in the upper mesopelagic layer (UML, 100–600 m) are investigated using results from seven Earth System Models forced by a high greenhouse gas emission scenario. The models as a class represent the observation-based distribution of oxygen (O2) and carbon dioxide (CO2), albeit major mismatches between observation-based and simulated values remain for individual models. By year 2100 all models project an increase in SST between 2 °C and 3 °C, and a decrease in the pH and in the saturation state of water with respect to calcium carbonate minerals in the UML. A decrease in the total ocean inventory of dissolved oxygen by 2% to 4% is projected by the range of models. Projected O2 changes in the UML show a complex pattern with both increasing and decreasing trends reflecting the subtle balance of different competing factors such as circulation, production, remineralization, and temperature changes. Projected changes in the total volume of hypoxic and suboxic waters remain relatively small in all models. A widespread increase of CO2 in the UML is projected. The median of the CO2 distribution between 100 and 600m shifts from 0.1–0.2 mol m−3 in year 1990 to 0.2–0.4 mol m−3 in year 2100, primarily as a result of the invasion of anthropogenic carbon from the atmosphere. The co-occurrence of changes in a range of environmental variables indicates the need to further investigate their synergistic impacts on marine ecosystems and Earth System feedbacks.

Description: Phytoplankton and bacteria are sensitive indicators of environmental change. The temporal development of these key organisms was monitored from 1988 to the end of 2007 at the time series station Boknis Eck in the western Baltic Sea. This period was characterized by the adaption of the Baltic Sea ecosystem to changes in the environmental conditions caused by the conversion of the political system in the southern and eastern border states, accompanied by the general effects of global climate change. Measured variables were chlorophyll, primary production, bacteria number, -biomass and -production, glucose turnover rate, macro-nutrients, pH, temperature and salinity. Negative trends with time were recorded for chlorophyll, bacteria number, bacterial biomass and bacterial production, nitrate, ammonia, phosphate, silicate, oxygen and salinity while temperature, pH, and the ratio between bacteria numbers and chlorophyll increased. Strongest reductions with time occurred for the annual maximum values, e.g. for chlorophyll during the spring bloom or for nitrate during winter, while the annual minimum values remained more stable. In deep water above sediment the negative trends of oxygen, nitrate, phosphate and bacterial variables as well as the positive trend of temperature were similar to those in the surface while the trends of salinity, ammonia and silicate were opposite to those in the surface. Decreasing oxygen, even in the surface layer, was of particular interest because it suggested enhanced recycling of nutrients from the deep hypoxic zones to the surface by vertical mixing. The long-term seasonal patterns of all variables correlated positively with temperature, except chlorophyll and salinity. Salinity correlated negatively with all bacterial variables (as well as precipitation) and positively with chlorophyll. Surprisingly, bacterial variables did not correlate with chlorophyll, which may be inherent with the time lag between the peaks of phytoplankton and bacteria during spring. Compared to the 20-yr averages of the environmental and microbial variables, the strongest negative deviations of corresponding annual averages were measured about ten years after political change for nitrate and bacterial secondary production (~ −60%), followed by chlorophyll (−50%) and bacterial biomass (−40%). Considering the circulation of surface currents in the Baltic Sea we interpret the observed patterns of the microbial variables at the Boknis Eck time series station as a consequence of the improved management of water resources after 1989 and – to a minor extent – the trends of the climate variables salinity and temperature.

Description: A new system for continuous, highly-resolved oceanic and atmospheric measurements of N2O, CO and CO2 is described. The system is based upon off-axis integrated cavity output spectroscopy (OA-ICOS) and a non-dispersive infrared analyzer (NDIR) both coupled to a Weiss-type equilibrator. Performance of the combined setup was evaluated by testing its precision, accuracy, long-term stability, linearity and response time. Furthermore, the setup was tested during two oceanographic campaigns in the equatorial Atlantic Ocean in order to explore its potential for autonomous deployment onboard voluntary observing ships (VOS). Improved equilibrator response times for N2O (2.5 min) and CO (45 min) were achieved in comparison to response times from similar chamber designs used by previous studies. High stability of the OA-ICOS analyzer was demonstrated by low optimal integration times of 2 and 4 min for N2O and CO respectively, as well as detection limits of 〈 40 ppt and precision better than 0.3 ppb Hz−1/2. Results from a direct comparison of the method presented here and well-established discrete methods for oceanic N2O and CO2 measurements showed very good consistency. The favorable agreement between underway atmospheric N2O, CO and CO2 measurements and monthly means at Ascension Island (7.96°S 14.4°W) further suggests a reliable operation of the underway setup in the field. The potential of the system as an improved platform for measurements of trace gases was explored by using continuous N2O and CO2 data to characterize the development of the seasonal equatorial upwelling in the Atlantic Ocean during two RV/ Maria S. Merian cruises. A similar record of high-resolution CO measurements was simultaneously obtained offering for the first time the possibility of a comprehensive view on the distribution and emissions of these climate relevant gases on the area. The relatively simple underway N2O/CO/CO2 setup is suitable for long-term deployment on board of research and commercial vessels although potential sources of drift such as cavity temperature and further technical improvements towards automation still need to be addressed.

Description: During the DRIVE (Diurnal and Regional Variability of Halogen Emissions) ship campaign we investigated the variability of the halogenated very short-lived substances (VSLS) bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) in the marine atmospheric boundary layer in the eastern tropical and subtropical North Atlantic Ocean during May/June 2010. The highest VSLS mixing ratios were found near the Mauritanian coast and close to Lisbon (Portugal). With backward trajectories we identified predominantly air masses from the open North Atlantic with some coastal influence in the Mauritanian upwelling area, due to the prevailing NW winds. The maximum VSLS mixing ratios above the Mauritanian upwelling were 8.92 ppt for bromoform, 3.14 ppt for dibromomethane and 3.29 ppt for methyl iodide, with an observed maximum range of the daily mean up to 50% for bromoform, 26% for dibromomethane and 56% for methyl iodide. The influence of various meteorological parameters - such as wind, surface air pressure, surface air and surface water temperature, humidity and marine atmospheric boundary layer (MABL) height - on VSLS concentrations and fluxes was investigated. The strongest relationship was found between the MABL height and bromoform, dibromomethane and methyl iodide abundances. Lowest MABL heights above the Mauritanian upwelling area coincide with highest VSLS mixing ratios and vice versa above the open ocean. Significant high anti-correlations confirm this relationship for the whole cruise. We conclude that especially above oceanic upwelling systems, in addition to sea-air fluxes, MABL height variations can influence atmospheric VSLS mixing ratios, occasionally leading to elevated atmospheric abundances. This may add to the postulated missing VSLS sources in the Mauritanian upwelling region (Quack et al., 2007).

Description: We have investigated the impact of assumed nitrous oxide (N2O) increases on stratospheric chemistry and dynamics by a series of idealized simulations. In a future cooler stratosphere the net yield of NOy from a changed N2O is known to decrease, but NOy can still be significantly increased by the increase of N2O. Results with a coupled chemistry-climate model (CCM) show that increases in N2O of 50%/100% between 2001 and 2050 result in more ozone destruction, causing a reduction in ozone mixing ratios of maximally 6%/10% in the middle stratosphere at around 10 hPa. This enhanced destruction could cause an ozone decline in the second half of this century in the middle stratosphere. However, the total ozone column still shows an increase in future decades, though the increase of 50%/100% in N2O caused a 2%/6% decrease in TCO compared with the reference simulation. N2O increases have significant effects on ozone trends at 20–10 hPa in the tropics and at northern high latitude, but have no significant effect on ozone trends in the Antarctic stratosphere. The ozone depletion potential for N2O in a future climate depends both on stratospheric temperature changes and tropospheric N2O changes, which have reversed effects on ozone in the middle and upper stratosphere. A 50% CO2 increase in conjunction with a 50% N2O increase cause significant ozone depletion in the middle stratosphere and lead to an increase of ozone in the upper stratosphere. Based on the multiple linear regression analysis and a series of sensitivity simulations, we find that the chemical effect of N2O increases dominates the ozone changes in the stratosphere while the dynamical and radiative effects of N2O increases are insignificant on average. However, the dynamical effect of N2O increases may cause large local changes in ozone mixing ratios, particularly, in the Southern Hemisphere lower stratosphere.

Description: A maximum in the strength of Agulhas leakage has been registered at the interface between the Indian and South Atlantic oceans during glacial Termination II (T-II). This presumably transported the salt and heat necessary for maintaining the Atlantic circulation at rates similar to the present day. However, it was never shown whether these waters were effectively incorporated into the South Atlantic gyre, or whether they retroflected into the Indian and/or Southern oceans. To resolve this question, we investigate the presence of paleo Agulhas rings from a sediment core on the central Walvis Ridge, almost 1800 km farther into the Atlantic Basin than previously studied. Analysis of a 60 yr data set from the global-nested INALT01 model allows us to relate density perturbations at the depth of the thermocline to the passage of individual rings over the core site. Using this relation from the numerical model as the basis for a proxy, we generate a time series of variability of individual Globorotalia truncatulinoides delta O-18. We reveal high levels of pycnocline depth variability at the site, suggesting enhanced numbers of Agulhas rings moving into the South Atlantic Gyre around T-II. Our record closely follows the published quantifications of Agulhas leakage from the east of the Cape Basin, and thus shows that Indian Ocean waters entered the South Atlantic circulation. This provides crucial support for the view of a prominent role of the Agulhas leakage in the shift from a glacial to an interglacial mode of the Atlantic circulation.

Description: he anthropogenic increase of carbon dioxide (CO2) alters the seawater carbonate chemistry, with a decline of pH and an increase in the partial pressure of CO2 (pCO2). Although bacteria play a major role in carbon cycling, little is known about the impact of rising pCO2 on bacterial carbon metabolism, especially for natural bacterial communities. In this study, we investigated the effect of rising pCO2 on bacterial production (BP), bacterial respiration (BR) and bacterial carbon metabolism during a mesocosm experiment performed in Kongsfjorden (Svalbard) in 2010. Nine mesocosms with pCO2 levels ranging from ca. 180 to 1400 μatm were deployed in the fjord and monitored for 30 days. Generally BP gradually decreased in all mesocosms in an initial phase, showed a large (3.6-fold average) but temporary increase on day 10, and increased slightly after inorganic nutrient addition. Over the wide range of pCO2 investigated, the patterns in BP and growth rate of bulk and free-living communities were generally similar over time. However, BP of the bulk community significantly decreased with increasing pCO2 after nutrient addition (day 14). In addition, increasing pCO2 enhanced the leucine to thymidine (Leu : TdR) ratio at the end of experiment, suggesting that pCO2 may alter the growth balance of bacteria. Stepwise multiple regression analysis suggests that multiple factors, including pCO2, explained the changes of BP, growth rate and Leu : TdR ratio at the end of the experiment. In contrast to BP, no clear trend and effect of changes of pCO2 was observed for BR, bacterial carbon demand and bacterial growth efficiency. Overall, the results suggest that changes in pCO2 potentially influence bacterial production, growth rate and growth balance rather than the conversion of dissolved organic matter into CO2.

Description: Oceans are a net source of molecular hydrogen (H-2) to the atmosphere, where nitrogen (N-2) fixation is assumed to be the main biological production pathway followed by photochemical production from organic material. The sources can be distinguished using isotope measurements because of clearly differing isotopic signatures of the produced hydrogen. Here we present the first ship-borne measurements of atmospheric molecular H-2 mixing ratio and isotopic composition at the West African coast of Mauritania (16-25 degrees W, 17-24 degrees N). This area is one of the biologically most active regions of the world's oceans with seasonal upwelling events and characterized by strongly differing hydrographical/ biological properties and phytoplankton community structures. The aim of this study was to identify areas of H-2 production and distinguish H-2 sources by isotopic signatures of atmospheric H-2. For this more than 100 air samples were taken during two cruises in February 2007 and 2008. During both cruises a transect from the Cape Verde Islands towards the Mauritanian Coast was sampled to cover differing oceanic regions such as upwelling and oligotrophic regimes. In 2007, additionally, four days were sampled at high resolution of one sample per hour to investigate a possible diurnal cycle of atmospheric H-2. Our results indicate the influence of local sources and suggest the Banc d'Arguin as a pool for precursors for photochemical H-2 production, whereas oceanic N-2 fixation could not be identified as a source for atmospheric H-2 during these two cruises. The variability in diurnal cycles is probably influenced by released precursors for photochemical H-2 production and also affected by a varying origin of air masses. This means for future investigations that only measuring the mixing ratio of H-2 is insufficient to explain the variability of an atmospheric diurnal cycle and support is needed, e.g. by isotopic measurements. Nevertheless, measurements of atmospheric H-2 mixing ratios, which are easy to conduct online during ship cruises, could be a useful indicator of production areas of biological precursors such as volatile organic compounds (VOCs) for further investigations.

Description: The shells of marine mollusks are widely used archives of past climate and ocean chemistry. Whilst the measurement of mollusk δ18O to develop records of past climate change is a commonly used approach, it has proven challenging to develop reliable independent paleothermometers that can be used to deconvolve the contributions of temperature and fluid composition on molluscan oxygen isotope compositions. Here we investigate the temperature dependence of 13C–18O bond abundance, denoted by the measured parameter Δ47, in shell carbonates of bivalve mollusks and assess its potential to be a useful paleothermometer. We report measurements on cultured specimens spanning a range in water temperatures of 5 to 25 °C, and field collected specimens spanning a range of −1 to 29 °C. In addition we investigate the potential influence of carbonate saturation state on bivalve stable isotope compositions by making measurements on both calcitic and aragonitic specimens that have been cultured in seawater that is either supersaturated or undersaturated with respect to aragonite. We find a robust relationship between Δ47 and growth temperature. We also find that the slope of a linear regression through all the Δ47 data for bivalves plotted against seawater temperature is significantly shallower than previously published inorganic and biogenic carbonate calibration studies produced in our laboratory and go on to discuss the possible sources of this difference. We find that changing seawater saturation state does not have significant effect on the Δ47 of bivalve shell carbonate in two taxa that we examined, and we do not observe significant differences between Δ47-temperature relationships between calcitic and aragonitic taxa.

Description: The aim of the present study was to compare preservation, staining and preparation techniques to assess the influence of different sample treatments and analyses on the accuracy of benthic foraminiferal assemblage data from NE Atlantic shelf seas. Replicate surface samples from the SE North Sea were preserved with ethanol–rose Bengal or formalin, some were stained after processing, or foraminifera were concentrated by flotation. Coloration of living specimens was different between samples treated with an ethanol–rose Bengal solution and those stained after washing. In the latter case, only the last two or three chambers were stained. The aliquot sample preserved with formalin showed dissolution features in agglutinated and porcellaneous species. Population density varied between different preservation, picking modes and investigators. The accuracy of picking was in the range of ±2 % (1σ), while external reproducibility ranged from –34 to +16 %. There was no significant difference between wet and dry picking. Samples that were concentrated by flotation generally yielded a lower number of specimens. Agglutinated species were underrepresented in samples that were stained after washing and in the flotation concentrate. Size fractions showed a reduction of population density and Fisher alpha diversity index with increasing mesh size. Only half of the specimens and less than two-thirds of the species are captured if the 〉125 μm rather than 〉63 μm fraction is analysed. In oxygen minimum zones, where small-sized species dominate the assemblage, the recovery in larger size fractions could be lower

Description: We carry out a case study of the transport and chemistry of bromoform and its product gases (PGs) in a sea breeze driven convective episode on 19 November 2011 along the North West coast of Borneo during the "Stratospheric ozone: Halogen Impacts in a Varying Atmosphere" (SHIVA) campaign. We use ground based, ship, aircraft and balloon sonde observations made during the campaign, and a 3-D regional online transport and chemistry model capable of resolving clouds and convection explicitly that includes detailed bromine chemistry. The model simulates the temperature, wind speed, wind direction fairly well for the most part, and adequately captures the convection location, timing, and intensity. The simulated transport of bromoform from the boundary layer up to 12 km compares well to aircraft observations to support our conclusions. The model makes several predictions regarding bromine transport from the boundary layer to the level of convective detrainment (11 to 12 km). First, the majority of bromine undergoes this transport as bromoform. Second, insoluble organic bromine carbonyl species are transported to between 11 and 12 km, but only form a small proportion of the transported bromine. Third, soluble bromine species, which include bromine organic peroxides, hydrobromic acid (HBr), and hypobromous acid (HOBr), are washed out efficiently within the core of the convective column. Fourth, insoluble inorganic bromine species (principally Br2) are not washed out of the convective column, but are also not transported to the altitude of detrainment in large quantities. We expect that Br2 will make a larger relative contribution to the total vertical transport of bromine atoms in scenarios with higher CHBr3 mixing ratios in the boundary layer, which have been observed in other regions. Finally, given the highly detailed description of the chemistry, transport and washout of bromine compounds within our simulations, we make a series of recommendations about the physical and chemical processes that should be represented in 3-D chemical transport models (CTMs) and chemistry climate models (CCMs), which are the primary theoretical means of estimating the contribution made by CHBr3 and other very short-lived substances (VSLS) to the stratospheric bromine budget.

Description: Microbial nitrous oxide (N2O) production in the ocean is enhanced under low-oxygen (O2) conditions. This is especially important in the context of increasing hypoxia (i.e., oceanic zones with extremely reduced O2 concentrations). Here, we present a study on the interannual variation in summertime nitrous oxide (N2O) concentrations in the bottom waters of the northern Gulf of Mexico (nGOM), which is well-known as the site of the second largest seasonally occurring hypoxic zone worldwide. To this end we developed a simple model that computes bottom-water N2O concentrations with a tri-linear 1N2O/O2 relationship based on water-column O2 concentrations, derived from summer (July) Texas–Louisiana shelf-wide hydrographic data between 1985 and 2007. 1N2O (i.e., excess N2O) was computed including nitrification and denitrification as the major microbial production and consumption pathways of N2O. The mean modeled bottom-water N2O concentration for July in the nGOM was 14.5±2.3 nmol L−1 (min: 11.0±4.5 nmol L−1 in 2000 and max: 20.6±11.3 nmol L−1 in 2002). The mean bottom-water N2O concentrations were significantly correlated with the areal extent of hypoxia in the nGOM. Our modeling analysis indicates that the nGOM is a persistent summer source of N2O, and nitrification is dominating N2O production in this region. Based on the ongoing increase in the areal extent of hypoxia in the nGOM, we conclude that N2O production (and its subsequent emissions)from this environmentally stressed region will probably continue to increase into the future.

Description: The Apparent Oxygen Utilisation (AOU) is a classical measure of the amount of oxygen respired in the ocean's interior. We show that AOU systematically overestimates True Oxygen Utilisation (TOU) in 6 coupled circulation-biogeochemical ocean models. This is due to atmosphere–ocean oxygen disequilibria in the subduction regions, consistent with previous work. We develop a simple, new, observationally-based approach which we call Evaluated Oxygen Utilisation (EOU). In this approach, we take into account the impact of the upper ocean oxygen disequilibria into the interior, considering that transport takes place predominantly along isopycnal surfaces. The EOU approximates the TOU with less than half of the bias of AOU in all 6 models despite large differences in the physical and biological components of the models. Applying the EOU approach to a global observational dataset yields an oxygen consumption rate 25% lower than that derived from AOU-based estimates, for a given ventilation rate.

Description: Although of substantial importance for marine tracer distributions and eventually global carbon, oxygen, and nitrogen fluxes, the interaction between sinking and remineralization of organic matter, benthic fluxes and burial is not always represented consistently in global biogeochemical models. We here aim to investigate the relationships between these processes with a suite of global biogeochemical models, each simulated over millennia, and compared against observed distributions of pelagic tracers and benthic and pelagic fluxes. We concentrate on the representation of sediment–water interactions in common numerical models, and investigate their potential impact on simulated global sediment–water fluxes and nutrient and oxygen distributions. We find that model configurations with benthic burial simulate global oxygen well over a wide range of possible sinking flux parameterizations, making the model more robust with regard to uncertainties about the remineralization length scale. On a global scale, burial mostly affects oxygen in the meso- to bathypelagic zone. While all model types show an almost identical fit to observed pelagic particle flux, and the same sensitivity to particle sinking speed, comparison to observational estimates of benthic fluxes reveals a more complex pattern, but definite interpretation is not straightforward because of heterogeneous data distribution and methodology. Still, evaluating model results against observed pelagic and benthic fluxes of organic matter can complement model assessments based on more traditional tracers such as nutrients or oxygen. Based on a combined metric of dissolved tracers and biogeochemical fluxes, we here identify two model descriptions of burial as suitable candidates for further experiments and eventual model refinements.

Description: Remote sensing via differential optical absorption spectroscopy (DOAS) has become a standard technique to identify and quantify trace gases in the atmosphere. Due to the wide range of measurement conditions, atmospheric compositions and instruments used, a specific challenge of a DOAS retrieval is to optimize the retrieval parameters for each specific case and particular trace gas of interest. Of these parameters, the retrieval wavelength range is one of the most important ones. Although for many trace gases the overall dependence of common DOAS retrieval on the evaluation wavelength interval is known, a systematic approach for finding the optimal retrieval wavelength range and quantitative assessment is missing. Here we present a novel tool to visualize the effect of different evaluation wavelength ranges. It is based on mapping retrieved column densities in the retrieval wavelength space and thus visualizing the consequences of different choices of spectral retrieval ranges caused by slightly erroneous absorption cross sections, cross correlations and instrumental features. Based on the information gathered, an optimal retrieval wavelength range may be determined systematically.

Description: The global ocean is a significant sink for anthropogenic carbon (C-ant), absorbing roughly a third of human CO2 emitted over the industrial period. Robust estimates of the magnitude and variability of the storage and distribution of C-ant in the ocean are therefore important for understanding the human impact on climate. In this synthesis we review observational and model-based estimates of the storage and transport of C-ant in the ocean. We pay particular attention to the uncertainties and potential biases inherent in different inference schemes. On a global scale, three data-based estimates of the distribution and inventory of C-ant are now available. While the inventories are found to agree within their uncertainty, there are considerable differences in the spatial distribution. We also present a review of the progress made in the application of inverse and data assimilation techniques which combine ocean interior estimates of C-ant with numerical ocean circulation models. Such methods are especially useful for estimating the air-sea flux and interior transport of C-ant, quantities that are otherwise difficult to observe directly. However, the results are found to be highly dependent on modeled circulation, with the spread due to different ocean models at least as large as that from the different observational methods used to estimate C-ant. Our review also highlights the importance of repeat measurements of hydro-graphic and biogeochemical parameters to estimate the storage of C-ant on decadal timescales in the presence of the variability in circulation that is neglected by other approaches. Data-based C-ant estimates provide important constraints on forward ocean models, which exhibit both broad similarities and regional errors relative to the observational fields. A compilation of inventories of C-ant gives us a "best" estimate of the global ocean inventory of anthropogenic carbon in 2010 of 155 +/- 31 PgC (+/- 20% uncertainty). This estimate includes a broad range of values, suggesting that a combination of approaches is necessary in order to achieve a robust quantification of the ocean sink of anthropogenic CO2.

Description: The global marine nitrogen cycle is constrained by nitrogen fixation as a source of reactive nitrogen, and denitrification or anammox on the sink side. These processes with their respective isotope effects set the marine nitrate N-15-isotope value (delta N-15) to a relatively constant average of 5 parts per thousand. This value can be used to better assess the magnitude of these sources and sink terms, but the underlying assumption is that sedimentary denitrification and anammox, processes responsible for approximately one-third of global nitrogen removal, have little to no isotope effect on nitrate in the water column. We investigated the isotope fractionation in sediment incubations, measuring net denitrification and nitrogen and oxygen stable isotope fractionation in surface sediments from the coastal Baltic Sea (Boknis Eck, northern Germany), a site with seasonal hypoxia and dynamic nitrogen turnover. Sediment denitrification was fast, and regardless of current paradigms assuming little fractionation during sediment denitrification, we measured fractionation factors of 18.9 parts per thousand for nitrogen and 15.8 parts per thousand for oxygen in nitrate. While the input of nitrate to the water column remains speculative, these results challenge the current view of fractionation during sedimentary denitrification and imply that nitrogen budget calculations may need to consider this variability, as both preferential uptake of light nitrate and release of the remaining heavy fraction can significantly alter water column nitrate isotope values at the sediment-water interface.

Description: The effect of ocean acidification on the balance between gross community production (GCP) and community respiration (CR) (i.e., net community production, NCP) of plankton communities was investigated in summer 2010 in Kongsfjorden, west of Svalbard. Surface water, which was characterized by low concentrations of dissolved inorganic nutrients and chlorophyll a (a proxy of phytoplankton biomass), was enclosed in nine mesocosms and subjected to eight pCO2 levels (two replicated controls and seven enhanced pCO2 treatments) for one month. Nutrients were added to all mesocosms on day 13 of the experiment, and thereafter increase of chlorophyll a was provoked in all mesocosms. No clear trend in response to increasing pCO2 was found in the daily values of NCP, CR, and GCP. For further analysis, these parameters were cumulated for the following three periods: phase 1 – end of CO2 manipulation until nutrient addition (t4 to t13); phase 2 – nutrient addition until the second chlorophyll a minimum (t14 to t21); phase 3 – the second chlorophyll a minimum until the end of this study (t22 to t28). A significant response was detected as a decrease of NCP with increasing pCO2 during phase 3. CR was relatively stable throughout the experiment in all mesocosms. As a result, the cumulative GCP significantly decreased with increasing pCO2 during phase 3. After the nutrient addition, the ratios of cumulative NCP to cumulative consumption of NO3 and PO4 showed a significant decrease during phase 3 with increasing pCO2. The results suggest that elevated pCO2 influenced cumulative NCP and stoichiometric C and nutrient coupling of the plankton community in a high-latitude fjord only for a limited period. However provided that there were some differences or weak correlations between NCP data based on different methods in the same experiment, this conclusion should be taken with caution.

Description: Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidizing capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38%) to 0.78 (115%) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24%) to 1.25 (167%) ppt. We also use aircraft observations made during the 2011 "Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere" (SHIVA) campaign, in the tropical West Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (BryVSLS). Our simulations show BryVSLS ranges from ~ 4.0 to 8.0 ppt depending on the inventory. We report an optimised estimate at the lower end of this range (~ 4 ppt) based on combining the CHBr3 and CH2Br2 inventories which give best agreement with the compilation of observations in the tropics.

Description: Mesoscale eddies seem to play an important role for both the hydrography and biogeochemistry of the eastern tropical Pacific Ocean (ETSP) off Peru. However, detailed surveys of these eddies are not available, which has so far hampered an in depth understanding of their implications for nutrient distribution and biological productivity. In this study, three eddies along a section at 16°45´ S have been surveyed intensively during R/V Meteor cruise M90 in November 2012. A coastal mode water eddy, an open ocean mode water eddy and an open ocean cyclonic eddy have been identified and sampled in order to determine both their hydrographic properties and their influence on the biogeochemical setting of the ETSP. In the thermocline the temperature of the coastal anticyclonic eddy was up to 2 °C warmer, 0.2 more saline and the swirl velocity was up to 35 cm s−1. The observed temperature and salinity anomalies, as well as swirl velocities of both types of eddies were about twice as large as had been described for the mean eddies in the ETSP. The observed heat and salt anomalies (AHA, ASA) of the anticyclonic eddy near the shelf-break of 17.7 × 1018 J and 36.6 × 1010 kg are more than twice as large as the mean AHA and ASA for the ETSP. We found that the eddies contributed to the productivity by maintaining pronounced subsurface maxima of chlorophyll of up to 6 μg L−1. Based on a comparison of the coastal (young) mode water eddy and the open ocean (old) mode water eddy we suggest that the ageing of eddies when they detach from the shelf-break and move westward to the open ocean influences the eddies' properties: chlorophyll maxima are reduced to about half (2.5–3 μg L−1) and nutrients are subducted. However, different settings at the time of formation may also contribute to the observed differences between the young and old mode water eddies. The coastal mode water eddy was found to be a site of nitrogen (N) loss in the OMZ with a maximum ΔNO3− anomaly (i.e. N loss) of about −25 μmol L−1 in 250 m water depth, whereas, the open ocean mode water and cyclonic eddies were of minor and negligible importance for the N loss, respectively. Our results show that the important role of eddies for the distribution of nutrients, as well as biogeochemical processes in the ETSP (and other OMZ/upwelling regions) can only be fully deciphered and understood through dedicated high spatial and temporal resolution oceanographic/biogeochemical surveys.

Description: Total dissolved inorganic carbon (CT) is one of the most frequently measured parameters used to calculate the partial pressure of carbon dioxide in seawater. Its determination has become increasingly important because of the rising interest in the biological effects of ocean acidification. Coulometric and infrared detection methods are currently favored in order to precisely quantify CT. These methods however are not sufficiently validated for CT measurements of biological experiments manipulating seawater carbonate chemistry with an extended CT measurement range (~1250–2400 μmol kg–1) compared to natural open ocean seawater (~1950–2200 μmol kg−1). The requirement of total sample amounts between 0.1–1 L seawater in the coulometric- and infrared detection methods potentially exclude their use for experiments working with much smaller volumes. Additionally, precise CT analytics become difficult with high amounts of biomass (e.g., phytoplankton cultures) or even impossible in the presence of planktonic calcifiers without sample pre-filtration. Filtration however, can alter CT concentration through gas exchange induced by high pressure. Addressing these problems, we present precise quantification of CT using a small, basic and inexpensive gas chromatograph as a CT analyzer. Our technique is able to provide a repeatability of ±3.1 μmol kg−1, given by the pooled standard deviation over a CT range typically applied in acidification experiments. 200 μL of sample is required to perform the actual CT measurement. The total sample amount needed is 12 mL. Moreover, we show that sample filtration is applicable with only minor alteration of the CT. The method is simple, reliable and with low cumulative material costs. Hence, it is potentially attractive for all researchers experimentally manipulating the seawater carbonate system.

Description: The effects of climate change on Arctic marine ecosystems and their biogeochemical cycles are difficult to predict given the complex physical, biological and chemical interactions among the ecosystem components. We studied benthic biogeochemical fluxes in the Arctic and the influence of short-term (seasonal to annual), long-term (annual to decadal) and other environmental variability on their spatial distribution to provide a baseline for estimates of the impact of future changes. In summer 2009, we measured fluxes of dissolved oxygen, nitrate, nitrite, ammonia, soluble reactive phosphate and silicic acid at the sediment–water interface at eight sites in the southeastern Beaufort Sea at water depths from 45 to 580 m. The spatial pattern of the measured benthic boundary fluxes was heterogeneous. Multivariate analysis of flux data showed that no single or reduced combination of fluxes could explain the majority of spatial variation, indicating that oxygen flux is not representative of other nutrient sink–source dynamics. We tested the influence of eight environmental parameters on single benthic fluxes. Short-term environmental parameters (sinking flux of particulate organic carbon above the bottom, sediment surface Chl a) were most important for explaining oxygen, ammonium and nitrate fluxes. Long-term parameters (porosity, surface manganese and iron concentration, bottom water oxygen concentrations) together with δ13Corg signature explained most of the spatial variation in phosphate, nitrate and nitrite fluxes. Variation in pigments at the sediment surface was most important to explain variation in fluxes of silicic acid. In a model including all fluxes synchronously, the overall spatial distribution could be best explained (57%) by the combination of sediment Chl a, phaeopigments, δ13Corg, surficial manganese and bottom water oxygen concentration. We conclude that it is necessary to consider long-term environmental variability along with rapidly ongoing environmental changes to predict the flux of oxygen and nutrients across Arctic sediments even at short timescales. Our results contribute to improve ecological models predicting the impact of climate change on the functioning of marine ecosystems.

Description: An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles is presented. The method is based on derivatization with o-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD 〈 10%), sensitivity (detection limits in the low ng L−1 range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the Polarstern cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulk water (BW) with average concentrations of 228 ng L−1 (GLY) and 196 ng L−1 (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng m−3) and MGLY (average concentration 0.15 ng m−3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosol particles could be a hint for interactions, in particular of GLY, between seawater and the atmosphere.

Description: The very thin sea surface nanolayer on top of the sea surface microlayer, sometimes just one monomolecular layer thick, forms the interface between ocean and atmosphere. Due to the small dimension and tiny amount of substance, knowledge about the development of the layer in the course of the year is scarce. In this work, the sea surface nanolayer at Boknis Eck Time Series Station (BE), southwestern Baltic Sea, has been investigated over a period of three and a half years. Surface water samples were taken monthly by screen sampling and were analyzed in terms of organic content and composition by sum frequency generation spectroscopy, which is specifically sensitive to interfacial layers. A yearly periodicity has been observed with a pronounced abundance of sea surface nanolayer material(such as carbohydrate-rich material) during the summer months. On the basis of our results we conclude that the abundance of organic material in the nanolayer at Boknis Eck is not directly related to phytoplankton abundance alone. We speculate that indeed sloppy feeding of zooplankton together with photochemical and/or microbial processing of organic precursor compounds is responsible for the pronounced seasonality.

Description: We used piston cores recovered in the western Bering Sea to reconstruct millennial-scale changes in marine productivity and terrigenous matter supply over the past similar to 180 kyr. Based on a geochemical multi-proxy approach, our results indicate closely interacting processes controlling marine productivity and terrigenous matter supply comparable to the situation in the Okhotsk Sea. Overall, terrigenous inputs were high, whereas export production was low. Minor increases in marine productivity occurred during intervals of Marine Isotope Stage 5 and interstadials, but pronounced maxima were recorded during interglacials and Termination I. The terrigenous material is suggested to be derived from continental sources on the eastern Bering Sea shelf and to be subsequently transported via sea ice, which is likely to drive changes in surface productivity, terrigenous inputs, and upper-ocean stratification. From our results we propose glacial, deglacial, and interglacial scenarios for environmental change in the Bering Sea. These changes seem to be primarily controlled by insolation and sea-level forcing which affect the strength of atmospheric pressure systems and sea-ice growth. The opening history of the Bering Strait is considered to have had an additional impact. High-resolution core logging data (color b*, XRF scans) strongly correspond to the Dansgaard-Oeschger climate variability registered in the NGRIP ice core and support an atmospheric coupling mechanism of Northern Hemisphere climates.

Description: This study focused on biogeochemical processes and microbial activity in sediments of a natural deep-sea CO2 seepage area (Yonaguni Knoll IV hydrothermal system, Japan). The aim was to assess the influence of the geochemical conditions occurring in highly acidic and CO2 saturated sediments on sulfate reduction (SR) and anaerobic methane oxidation (AOM). Porewater chemistry was investigated from retrieved sediment cores and in situ by microsensor profiling. The sites sampled around a sediment-hosted hydrothermal CO2 vent were very heterogeneous in porewater chemistry, indicating a complex leakage pattern. Near the vents, droplets of liquid CO2 were observed emanating from the sediments, and the pH reached approximately 4.5 in a sediment depth 〉 6 cm, as determined in situ by microsensors. Methane and sulfate co-occurred in most sediment samples from the vicinity of the vents down to a depth of 3 m. However, SR and AOM were restricted to the upper 7-15 cm below seafloor, although neither temperature, low pH, nor the availability of methane and sulfate could be limiting microbial activity. We argue that the extremely high subsurface concentrations of dissolved CO2 (1000-1700 mM), which disrupt the cellular pH homeostasis, and lead to end-product inhibition. This limits life to the surface sediment horizons above the liquid CO2 phase, where less extreme conditions prevail. Our results may have to be taken into consideration in assessing the consequences of deep-sea CO2 sequestration on benthic element cycling and on the local ecosystem state.

Description: About 30% of the anthropogenically released CO2 is taken up by the oceans; such uptake causes surface ocean pH to decrease and is commonly referred to as ocean acidification (OA). Foraminifera are one of the most abundant groups of marine calcifiers, estimated to precipitate ca. 50 % of biogenic calcium carbonate in the open oceans. We have compiled the state of the art literature on OA effects on foraminifera, because the majority of OA research on this group was published within the last three years. Disparate responses of this important group of marine calcifiers to OA were reported, highlighting the importance of a process-based understanding of OA effects on foraminifera. We cultured the benthic foraminifer Ammonia sp. under a range of carbonate chemistry manipulation treatments to identify the parameter of the carbonate system causing the observed effects. This parameter identification is the first step towards a process-based understanding. We argue that [CO32−] is the parameter affecting foraminiferal size-normalized weights (SNWs) and growth rates. Based on the presented data, we can confirm the strong potential of Ammonia sp. foraminiferal SNW as a [CO32−] proxy.

Description: In recent years, an increasing number of studies on phytoplankton in the tropical South China Sea (SCS) and Sulu Sea (SS) have been conducted. However, still little is known about the photophysiological state of natural phytoplankton communities under varying environmental conditions. This study investigates the photophysiological state of natural phytoplankton communities in the southern SCS and SS based on high horizontal and vertical resolution field observations collected during the SHIVA (Stratosphere ozone: Halogens in a Varying Atmosphere) cruise (SO 218) in November 2011 on board RV Sonne. At the surface, pigment results revealed that total chlorophyll a (TChl a ) concentrations at all offshore stations were low at the surface and were generally dominated by cyanobacteria. Enhanced concentrations of TChl a were only observed below the upper mixed layer and above the euphotic depth with haptophytes, prochlorophytes and prasinophytes contributing most of the biomass. At stations close to the coast and river outflows, surface phytoplankton blooms (between 1 to 2.2 mg m−3) dominated by diatoms were observed. Overall, the study region exhibited strong nitrate + nitrite (NOx, 〈 1 μmol L−1), and phosphate (PO4, 〈 0.2 μmol L−1) depletion from surface down to about 50–60 m. Silicate (Si) exhibited similar trends with the exception of some near shore stations in which high Si concentrations (〉 2 μmol L−1) were observed in conjunction with increased TChl a and diatoms concentrations. Surface NOx concentrations were observed to correlate positively with temperature (τ = 0.22, p 〈 0.05, n = 108), whereas negative correlations were reported between surface NOx (τ = −0.27, p 〈 0.05, n = 108), Si (τ = −0.68, p 〈 0.05, n = 108) and salinity indicating that the enhancement in nutrients at the surface was probably supplied through fresher and warmer river waters near the coast. In contrast, the opposite was observed between temperature, salinity and all nutrients in the water column suggesting that nutrients were supplied from the bottom through upwelling. Pigment gradients show that phytoplankton were optimising their pigment composition to acclimate to changes in the light climate and cells were in a competent state as suggested by high maximum photochemical efficiency values (Fv/ Fm, 〉 0.4)

Description: A combined interpretation of synthetic aperture radar (SAR) satellite images and helicopter electromagnetic (HEM) sea-ice thickness data has provided an estimate of sea-ice volume formed in Laptev Sea polynyas during the winter of 2007/08. The evolution of the surveyed sea-ice areas, which were formed between late December 2007 and middle April 2008, was tracked using a series of SAR images with a sampling interval of 2–3 days. Approximately 160 km of HEM data recorded in April 2008 provided sea-ice thicknesses along profiles that transected sea ice varying in age from 1 to 116 days. For the volume estimates, thickness information along the HEM profiles was extrapolated to zones of the same age. The error of areal mean thickness information was estimated to be between 0.2 m for younger ice and up to 1.55 m for older ice, with the primary error source being the spatially limited HEM coverage. Our results have demonstrated that the modal thicknesses and mean thicknesses of level ice correlated with the sea-ice age, but that varying dynamic and thermodynamic sea-ice growth conditions resulted in a rather heterogeneous sea-ice thickness distribution on scales of tens of kilometers. Taking all uncertainties into account, total sea-ice area and volume produced within the entire surveyed area were 52 650 km2 and 93.6 ± 26.6 km3. The surveyed polynya contributed 2.0 ± 0.5% of the sea-ice produced throughout the Arctic during the 2007/08 winter. The SAR-HEM volume estimate compares well with the 112 km3 ice production calculated with a~high-resolution ocean sea-ice model. Measured modal and mean-level ice thicknesses correlate with calculated freezing-degree-day thicknesses with a factor of 0.87–0.89, which was too low to justify the assumption of homogeneous thermodynamic growth conditions in the area, or indicates a strong dynamic thickening of level ice by rafting of even thicker ice.

Description: Epibenthic megafauna play an important role in the deep-sea environment and contribute significantly to benthic biomass, but their population dynamics are still understudied. We used a towed deep-sea camera system to assess the population densities of epibenthic megafauna in 2002, 2007, and 2012 at the shallowest station (HG I, ∼1300 m) of the deep-sea observatory HAUSGARTEN, in the eastern Fram Strait. Our results indicate that the overall density of megafauna was significantly lower in 2007 than in 2002, but was significantly higher in 2012, resulting in overall greater megafaunal density in 2012. Different species showed different patterns in population density, but the relative proportions of predator/scavengers and suspension-feeding individuals were both higher in 2012. Variations in megafaunal densities and proportions are likely due to variation in food input to the sea floor, which decreased slightly in the years preceding 2007 and was greatly elevated in the years preceding 2012. Both average evenness and diversity increased over the time period studied, which indicates that HG I may be food-limited and subject to bottom-up control. The community of HG I may be unique in its response to elevated food input, which resulted in higher evenness and diversity in 2012.

Description: Ice core records demonstrate a glacial–interglacial atmospheric CO2 increase of ~ 100 ppm, while 14C calibration efforts document a strong decrease in atmospheric 14C concentration during this period. A calculated transfer of ~ 530 Gt of 14C-depleted carbon is required to produce the deglacial coeval rise of carbon in the atmosphere and terrestrial biosphere. This amount is usually ascribed to oceanic carbon release, although the actual mechanisms remained elusive, since an adequately old and carbon-enriched deep-ocean reservoir seemed unlikely. Here we present a new, though still fragmentary, ocean-wide Δ14C data set showing that during the Last Glacial Maximum (LGM) and Heinrich Stadial 1 (HS-1) the maximum 14C age difference between ocean deep waters and the atmosphere exceeded the modern values by up to 1500 14C yr, in the extreme reaching 5100 14C yr. Below 2000 m depth the 14C ventilation age of modern ocean waters is directly linked to the concentration of dissolved inorganic carbon (DIC). We propose as a working hypothesis that the modern regression of DIC vs. Δ14C also applies for LGM times, which implies that a mean LGM aging of ~ 600 14C yr corresponded to a global rise of ~ 85–115 μmol DIC kg−1 in the deep ocean. Thus, the prolonged residence time of ocean deep waters may indeed have made it possible to absorb an additional ~ 730–980 Gt DIC, one third of which possibly originated from intermediate waters. We also infer that LGM deep-water O2 dropped to suboxic values of 〈 10 μmol kg−1 in the Atlantic sector of the Southern Ocean, possibly also in the subpolar North Pacific. The deglacial transfer of the extra-aged, deep-ocean carbon to the atmosphere via the dynamic ocean–atmosphere carbon exchange would be sufficient to account for two trends observed, (1) for the increase in atmospheric CO2 and (2) for the 190‰ drop in atmospheric Δ14C during the so-called HS-1 "Mystery Interval", when atmospheric 14C production rates were largely constant

Description: Nitrite (NO2−) is a substrate for both oxidative and reductive microbial metabolism. NO2− accumulates at the base of the euphotic zone in oxygenated, stratified open-ocean water columns, forming a feature known as the primary nitrite maximum (PNM). Potential pathways of NO2− production include the oxidation of ammonia (NH3) by ammonia-oxidizing bacteria and archaea as well as assimilatory nitrate (NO3−) reduction by phytoplankton and heterotrophic bacteria. Measurements of NH3 oxidation and NO3− reduction to NO2− were conducted at two stations in the central California Current in the eastern North Pacific to determine the relative contributions of these processes to NO2− production in the PNM. Sensitive (〈 10 nmol L−1), precise measurements of NH4+ and NO2− indicated a persistent NH4+ maximum overlying the PNM at every station, with concentrations as high as 1.5 μmol L−1. Within and just below the PNM, NH3 oxidation was the dominant NO2− producing process, with rates of NH3 oxidation to NO2− of up to 31 nmol L-1 d-1, coinciding with high abundances of ammonia-oxidizing archaea. Though little NO2− production from NO3− was detected, potentially nitrate-reducing phytoplankton (photosynthetic picoeukaryotes, 〈i〉Synechococcus〈/i〉, and 〈i〉Prochlorococcus〈/i〉) were present at the depth of the PNM. Rates of NO2− production from NO3− were highest within the upper mixed layer (4.6 nmol L-1 d-1) but were either below detection limits or 10 times lower than NH3 oxidation rates around the PNM. One-dimensional modeling of water column NO2− production agreed with production determined from 15N bottle incubations within the PNM, but a modeled net biological sink for NO2− just below the PNM was not captured in the incubations. Residence time estimates of NO2− within the PNM ranged from 18 to 470 days at the mesotrophic station and was 40 days at the oligotrophic station. Our results suggest the PNM is a dynamic, rather than relict, feature with a source term dominated by ammonia oxidation. © 2013 Author(s).

Description: Water vapor plays an important role in meteorological applications; GeoForschungsZentrum (GFZ) therefore developed a tomographic system to derive 3-D distributions of the tropospheric water vapor above Germany using GPS data from about 300 ground stations. Input data for the tomographic reconstructions are generated by the Earth Parameter and Orbit determination System (EPOS) software of the GFZ, which provides zenith total delay (ZTD), integrated water vapor (IWV) and slant total delay (STD) data operationally with a temporal resolution of 2.5 min (STD) and 15 min (ZTD, IWV). The water vapor distribution in the atmosphere is derived by tomographic reconstruction techniques. The quality of the solution is dependent on many factors such as the spatial coverage of the atmosphere with slant paths, the spatial distribution of their intersections and the accuracy of the input observations. Independent observations are required to validate the tomographic reconstructions and to get precise information on the accuracy of the derived 3-D water vapor fields. To determine the quality of the GPS tomography, more than 8000 vertical water vapor profiles at 13 German radiosonde stations were used for the comparison. The radiosondes were launched twice a day (at 00:00 UTC and 12:00 UTC) in 2007. In this paper, parameters of the entire profiles such as the wet refractivity, and the zenith wet delay have been compared. Before the validation the temporal and spatial distribution of the slant paths, serving as a basis for tomographic reconstruction, as well as their angular distribution were studied. The mean wet refractivity differences between tomography and radiosonde data for all points vary from −1.3 to 0.3, and the root mean square is within the range of 6.5–9. About 32% of 6803 profiles match well, 23% match badly and 45% are difficult to classify as they match only in parts.

Description: In order to detect shifts in community structure and function associated with global change, the natural background fluctuation in these traits must be known. In a 6 yr study we characterized the composition of young benthic communities at 7 sites along the 300 km coast of the Kiel and Lübeck bights in the German Baltic Sea and we quantified their interannual variability of taxonomic and functional composition. Along the salinity gradient from NW to SE, the relative abundance of primary producers decreased while that of heterotrophs increased. Along the same gradient, annual productivity tended to increase. Taxonomic and functional richness were higher in Kiel Bight as compared to Lübeck Bight. With increasing species richness functional group richness showed saturation indicating an increasing functional redundancy in species rich communities. While taxonomic fluctuations between years were substantial, functionality of the communities seem preserved in most cases. Environmental conditions potentially driving these fluctuations are winter temperatures and current regimes. We tentatively define a confidence range of natural variability in taxonomic and functional composition a departure from which might help identifying an ongoing regime shift driven by global change. In addition, we propose to use RELATE, a statistical procedure in the PRIMER (Plymouth Routines in Multivariate Ecological Research) package to distinguish directional shifts in time ("signal") from natural temporal fluctuations ("noise")

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: The influence of various wind and wave conditions on the variability of downwelling irradiance Ed (490 nm) in water is subject of this study. The work is based on a two-dimensional Monte Carlo radiative transfer model with high spatial resolution. The model assumes conditions that are ideal for wave focusing, thus simulation results reveal the upper limit for light fluctuations. Local wind primarily determines the steepness of capillary-gravity waves which in turn dominate the irradiance variability near the surface. Down to 3 m depth, maximum irradiance peaks that exceed the mean irradiance Ed by a factor of more than 7 can be observed at low wind speeds up to 5 m s−1. The strength of irradiance fluctuations can be even amplified under the influence of higher ultra-gravity waves; thereby peaks can exceed 11 Ed. Sea states influence the light field much deeper; gravity waves can cause considerable irradiance variability even at 100 m depth. The simulation results show that under realistic conditions 50% radiative enhancements compared to the mean can still occur at 30 m depth. At greater depths, the underwater light variability depends on the wave steepness of the characteristic wave of a sea state; steeper waves cause stronger light fluctuations.

Description: The Arctic featured the strongest surface warming over the globe during the recent decades, and the temperature increase was accompanied by a rapid decline in sea ice extent. However, little is known about Arctic sea ice change during the Early Twentieth Century Warming (ETCW) during 1920–1940, also a period of a strong surface warming, both globally and in the Arctic. Here, we investigate the sensitivity of Arctic winter surface air temperature (SAT) to sea ice during 1875–2008 by means of simulations with an atmospheric general circulation model (AGCM) forced by estimates of the observed sea surface temperature (SST) and sea ice concentration. The Arctic warming trend since the 1960s is very well reproduced by the model. In contrast, ETCW in the Arctic is hardly captured. This is consistent with the fact that the sea ice extent in the forcing data does not strongly vary during ETCW. AGCM simulations with observed SST but fixed sea ice reveal a strong dependence of winter SAT on sea ice extent. In particular, the warming during the recent decades is strongly underestimated by the model, if the sea ice extent does not decline and varies only seasonally. This suggests that a significant reduction of Arctic sea ice extent may have also accompanied the Early Twentieth Century Warming, pointing toward an important link between anomalous sea ice extent and Arctic surface temperature variability.

Description: 2-D seismic data from the top and the western slope of Mergui Ridge in water depths between 300 and 2200 m off the Thai west coast have been investigated in order to identify mass transport deposits (MTDs) and evaluate the tsunamigenic potential of submarine landslides in this outer shelf area. Based on our newly collected data, 17 mass transport deposits have been identified. Minimum volumes of individual MTDs range between 0.3 km3 and 14 km3. Landslide deposits have been identified in three different settings: (i) stacked MTDs within disturbed and faulted basin sediments at the transition of the East Andaman Basin to the Mergui Ridge; (ii) MTDs within a pile of drift sediments at the basin-ridge transition; and (iii) MTDs near the edge of/on top of Mergui Ridge in relatively shallow water depths (〈 1000 m). Our data indicate that the Mergui Ridge slope area seems to have been generally unstable with repeated occurrence of slide events. We find that the most likely causes for slope instabilities may be the presence of unstable drift sediments, excess pore pressure, and active tectonics. Most MTDs are located in large water depths (〉 1000 m) and/or comprise small volumes suggesting a small tsunami potential. Moreover, the recurrence rates of failure events seem to be low. Some MTDs with tsunami potential, however, have been identified on top of Mergui Ridge. Mass-wasting events that may occur in the future at similar locations may trigger tsunamis if they comprise sufficient volumes. Landslide tsunamis, emerging from slope failures in the working area and affecting western Thailand coastal areas therefore cannot be excluded, though the probability is very small compared to the probability of earthquake-triggered tsunamis, arising from the Sunda Trench.

Description: Observations and model runs indicate trends in dissolved oxygen (DO) associated with current and ongoing global warming. However, a large-scale observation-to-model comparison has been missing and is presented here. This study presents a first global compilation of DO measurements covering the last 50 yr. It shows declining upper-ocean DO levels in many regions, especially the tropical oceans, whereas areas with increasing trends are found in the subtropics and in some subpolar regions. For the Atlantic Ocean south of 20° N, the DO history could even be extended back to about 70 yr, showing decreasing DO in the subtropical South Atlantic. The global mean DO trend between 50° S and 50° N at 300 dbar for the period 1960 to 2010 is –0.066 μmol kg−1 yr−1. Results of a numerical biogeochemical Earth system model reveal that the magnitude of the observed change is consistent with CO2-induced climate change. However, the pattern correlation between simulated and observed patterns of past DO change is negative, indicating that the model does not correctly reproduce the processes responsible for observed regional oxygen changes in the past 50 yr. A negative pattern correlation is also obtained for model configurations with particularly low and particularly high diapycnal mixing, for a configuration that assumes a CO2-induced enhancement of the C : N ratios of exported organic matter and irrespective of whether climatological or realistic winds from reanalysis products are used to force the model. Depending on the model configuration the 300 dbar DO trend between 50° S and 50° N is −0.027 to –0.047 μmol kg−1 yr−1 for climatological wind forcing, with a much larger range of –0.083 to +0.027 μmol kg−1 yr−1 for different initializations of sensitivity runs with reanalysis wind forcing. Although numerical models reproduce the overall sign and, to some extent, magnitude of observed ocean deoxygenation, this degree of realism does not necessarily apply to simulated regional patterns and the representation of processes involved in their generation. Further analysis of the processes that can explain the discrepancies between observed and modeled DO trends is required to better understand the climate sensitivity of oceanic oxygen fields and predict potential DO changes in the future.

Description: A 2-Dimensional mathematical reaction-transport model was developed to study the impact of the mud-dwelling frenulate tubeworm Siboglinum sp. on the biogeochemistry of a sediment (MUC15) at the Captain Arutyunov mud volcano (CAMV). By explicitly describing the worm in its surrounding sediment, we are able to make budgets of processes occurring in- or outside of the worm, and to quantify how different worm densities and biomasses affect the anaerobic oxidation of methane (AOM) and sulfide reoxidation (HSox). The model shows that, at the observed densities, the presence of a thin worm body is sufficient to keep the upper 10 cm of sediment well homogenised with respect to dissolved substances, in agreement with observations. By this "bio-ventilation" activity, the worm pushes the sulfate-methane transition (SMT) zone downward to the posterior end of its body, and simultaneously physically separates the sulfide produced during the anaerobic oxidation of methane from oxygen. While there is little scope for AOM to take place in the tubeworm's body, 70% of the sulfide that is produced by sulfate reduction processes or that is advected in the sediment is preferentially shunted via the organism where it is oxidised by endosymbionts providing the energy for the worm's growth. The process of sulfide reoxidation, occurring predominantly in the worm's body is thus very distinct from the anaerobic oxidation of methane, which is a diffuse process that takes place in the sediments in the methane-sulfate transition zone. We show how the sulfide oxidation process is affected by increasing densities and length of the frenulates, and by upward advection velocity. Our biogeochemical model is one of the first to describe tubeworms explicitly. It can be used to directly link biological and biogeochemical observations at seep sites, and to study the impacts of mud-dwelling frenulates on the sediment biogeochemistry under varying environmental conditions. Also, it provides a tool to explore the competition between bacteria and fauna for available energy resources.

Description: In the aftermath of an earthquake and tsunami on 11 March 2011 radioactive 137Cs was discharged from a damaged nuclear power plant to the sea off Fukushima Dai-ichi, Japan. Here we explore its dilution and fate with a state-of-the-art global ocean general circulation model, which is eddy-resolving in the region of interest. We find apparent consistency between our simulated circulation, estimates of 137Cs discharged ranging from 0.94 p Bq (Japanese Government, 2011) to 3.5 ± 0.7 p Bq (Tsumune et al., 2012), and measurements by Japanese authorities and the power plant operator. In contrast, our simulations are apparently inconsistent with the high 27 ± 15 p Bq discharge estimate of Bailly du Bois et al. (2012). Expressed in terms of a diffusivity we diagnose, from our simulations, an initial dilution on the shelf of 60 to 100 m2 s−1. The cross-shelf diffusivity is at 500 ± 300 m2 s−1 significantly higher and variable in time as indicated by its uncertainty. Expressed as an effective residence time of surface water on the shelf, the latter estimate transfers to 43 ± 16 days. As regards the fate of 137Cs, our simulations suggest that activities up to 4 mBq l−1 prevail in the Kuroshio-Oyashio Interfrontal Zone one year after the accident. This allows for low but detectable 0.1 to 0.3 m Bq l−1 entering the North Pacific Intermediate Water before the 137Cs signal is flushed away. The latter estimates concern the direct release to the sea only.

Description: The global Late Pliocene/Early Pleistocene cooling (~3.0–2.0 million years ago – Ma) concurred with extremely high diatom and biogenic opal production in most of the major coastal upwelling regions. This phenomenon was particularly pronounced in the Benguela upwelling system (BUS), off Namibia, where it is known as the Matuyama Diatom Maximum (MDM). Our study focuses on a new diatom silicon isotope (δ30Si) record covering the MDM in the BUS. Unexpectedly, the variations in δ30Si signal follow biogenic opal content, whereby the highest δ30Si values correspond to the highest biogenic opal content. We interpret the higher δ30Si values during the MDM as a result of a stronger degree of silicate utilisation in the surface waters caused by high productivity of mat-forming diatom species. This was most likely promoted by weak upwelling intensity dominating the BUS during the Late Pliocene/Early Pleistocene cooling combined with a large silicate supply derived from a strong Southern Ocean nutrient leakage responding to the expansion of Antarctic ice cover and the resulting stratification of the polar ocean 3.0–2.7 Ma ago. A similar scenario is hypothesized for other major coastal upwelling systems (e.g. off California) during this time interval, suggesting that the efficiency of the biological carbon pump was probably sufficiently enhanced in these regions during the MDM to have significantly increased the transport of atmospheric CO2 to the deep ocean. In addition, the coeval extension of the area of surface water stratification in both the Southern Ocean and the North Pacific, which decreased CO2 release to the atmosphere, led to further enhanced atmospheric CO2 drawn-down and thus contributed significantly to Late Pliocene/Early Pleistocene cooling.

Description: Oxygen-deficient waters in the ocean, generally referred to as oxygen minimum zones (OMZ), are expected to expand as a consequence of global climate change. Poor oxygenation is promoting microbial loss of inorganic nitrogen (N) and increasing release of sediment-bound phosphate (P) into the water column. These intermediate water masses, nutrient-loaded but with an N deficit relative to the canonical N:P Redfield ratio of 16:1, are transported via coastal upwelling into the euphotic zone. To test the impact of nutrient supply and nutrient stoichiometry on production, partitioning and elemental composition of dissolved (DOC, DON, DOP) and particulate (POC, PON, POP) organic matter, three nutrient enrichment experiments were conducted with natural microbial communities in shipboard mesocosms, during research cruises in the tropical waters of the southeast Pacific and the northeast Atlantic. Maximum accumulation of POC and PON was observed under high N supply conditions, indicating that primary production was controlled by N availability. The stoichiometry of microbial biomass was unaffected by nutrient N:P supply during exponential growth under nutrient saturation, while it was highly variable under conditions of nutrient limitation and closely correlated to the N:P supply ratio, although PON:POP of accumulated biomass generally exceeded the supply ratio. Microbial N:P composition was constrained by a general lower limit of 5:1. Channelling of assimilated P into DOP appears to be the mechanism responsible for the consistent offset of cellular stoichiometry relative to inorganic nutrient supply and nutrient drawdown, as DOP build-up was observed to intensify under decreasing N:P supply. Low nutrient N:P conditions in coastal upwelling areas overlying O2-deficient waters seem to represent a net source for DOP, which may stimulate growth of diazotrophic phytoplankton. These results demonstrate that microbial nutrient assimilation and partitioning of organic matter between the particulate and the dissolved phase are controlled by the N:P ratio of upwelled nutrients, implying substantial consequences for nutrient cycling and organic matter pools in the course of decreasing nutrient N:P stoichiometry.

Description: Oceanic emissions of halogenated very short-lived substances (VSLS) are expected to contribute significantly to the stratospheric halogen loading and therefore to ozone depletion. The amount of VSLS transported into the stratosphere is estimated based on in-situ observations around the tropical tropopause layer (TTL) and on modeling studies which mostly use prescribed global emission scenarios to reproduce observed atmospheric concentrations. In addition to upper-air VSLS measurements, direct observations of oceanic VSLS emissions are available along ship cruise tracks. Here we use such in-situ observations of VSLS emissions from the West Pacific and tropical Atlantic together with an atmospheric Lagrangian transport model to estimate the direct contribution of bromoform (CHBr3), and dibromomethane (CH2Br2) to the stratospheric bromine loading as well as their ozone depletion potential. Our emission-based estimates of VSLS profiles are compared to upper-air observations and thus link observed oceanic emissions and in situ TTL measurements. This comparison determines how VSLS emissions and transport in the cruise track regions contribute to global upper-air VSLS estimates. The West Pacific emission-based profiles and the global upper-air observations of CHBr3 show a relatively good agreement indicating that emissions from the West Pacific provide an average contribution to the global CHBr3 budget. The tropical Atlantic, although also being a CHBr3 source region, is of less importance for global upper-air CHBr3 estimates as revealed by the small emission-based abundances in the TTL. Western Pacific CH2Br2 emission-based estimates are considerably smaller than upper-air observations as a result of the relatively low sea-to-air flux found in the West Pacific. Together, CHBr3 and CH2Br2 emissions from the West Pacific are projected to contribute to the stratospheric bromine budget with 0.4 pptv Br on average and 2.3 pptv Br for cases of maximum emissions through product and source gas injection. These relatively low estimates reveal that the tropical West Pacific, although characterized by strong convective transport, might overall contribute less VSLS to the stratospheric bromine budget than other regions as a result of only low CH2Br2 and moderate CHBr3 oceanic emissions.

Description: In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0–134.8 μmol mol−1 for the Fe/Ca and 1.68(±0.41) μmol mol−1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1σ[Mn/Ca] = 0.35–2.07 μmol mol−1; 1σ[Fe/Ca] = 93.9–188.4 μmol mol−1). The Mn/Ca ratios in the calcite were generally relatively low (2.21–9.93 μmol mol−1) but in the same magnitude and proportional to the surrounding pore waters (1.37–6.67 μmol mol−1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0–101.0 μmol mol−1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration.

Description: The aim of this study is to determine cloud-type resolved cloud radiative budgets and cloud radiative effects from surface measurements of broadband radiative fluxes over the Atlantic Ocean. Furthermore, based on simultaneous observations of the state of the cloudy atmosphere, a radiative closure study has been performed by means of the ECHAM5 single column model in order to identify the model's ability to realistically reproduce the effects of clouds on the climate system. An extensive database of radiative and atmospheric measurements has been established along five meridional cruises of the German research icebreaker Polarstern. Besides pyranometer and pyrgeometer for downward broadband solar and thermal radiative fluxes, a sky imager and a microwave radiometer have been utilized to determine cloud fraction and cloud type on the one hand and temperature and humidity profiles as well as liquid water path for warm non-precipitating clouds on the other hand. Averaged over all cruise tracks, we obtain a total net (solar + thermal) radiative flux of 144 W m(-2) that is dominated by the solar component. In general, the solar contribution is large for cirrus clouds and small for stratus clouds. No significant meridional dependencies were found for the surface radiation budgets and cloud effects. The strongest surface longwave cloud effects were shown in the presence of low level clouds. Clouds with a high optical density induce strong negative solar radiative effects under high solar altitudes. The mean surface net cloud radiative effect is -33 W m(-2). For the purpose of quickly estimating the mean surface longwave, shortwave and net cloud effects in moderate, subtropical and tropical climate regimes, a new parameterisation was created, considering the total cloud amount and the solar zenith angle. The ECHAM5 single column model provides a surface net cloud effect that is more cooling by 17 W m(-2) compared to the radiation observations. This overestimation in solar cooling is mostly caused by the shortwave impact of convective clouds. The latter show a large overestimation in solar cooling of up to 114 W m(-2). Mean cloud radiative effects of cirrus and stratus clouds were simulated close to the observations.

Description: The internal consistency of measurements and computations of components of the CO2-system, namely total alkalinity (AT), total dissolved carbon dioxide (CT), CO2 fugacity (fCO2), and pH, has been confirmed repeatedly in open ocean studies when the CO2 system had been over determined. Differences between measured and computed properties, such as ΔfCO2 (=fCO2(measured) – fCO2(computed from AT and CT))/ fCO2(measured)× 100), there are usually below 5%. Recently, Hoppe et al. (2010) provided evidence of significantly larger ΔfCO2 in experimental setups. These observations are currently not well understood. Here we discuss a case from a series of phytoplankton culture experiments with ΔfCO2 of up to about 25%. ΔfCO2 varied systematically during the course of these experiments and showed a clear correlation with the accumulation of dissolved organic carbon (DOC). Culture and mesocosm experiments are often carried out under very high initial nutrient concentrations, yielding high biomass concentrations that in turn often lead to a substantial build-up of DOC. DOC can reach concentrations much higher than typically observed in the open ocean. To the extent that DOC includes organic acids and bases, it will contribute to the alkalinity of the seawater contained in the experimental device. Our analysis suggests that whenever substantial amounts of DOC are produced during the experiment, standard computer programs used to compute CO2 fugacity can underestimate true fCO2 significantly when the computation is based on AT and CT. Alternative explanations for large ΔfCO2, e.g. uncertainties of pKs, are explored as well, but are found to be of minor importance. Unless the effect of DOC-alkalinity is accounted for, this might lead to significant errors in the interpretation of the system under consideration to the experimentally applied CO2 perturbation, which could misguide the development of parameterisations used in simulations with global carbon cycle models in future CO2-scenarios.

Description: Emiliania huxleyi (strain B 92/11) was exposed to different nutrient supply, CO2 and temperature conditions in phosphorus controlled chemostats to investigate effects on organic carbon exudation and partitioning between the pools of particulate organic carbon (POC) and dissolved organic carbon (DOC). 14C incubation measurements for primary production (PP) and extracellular release (ER) were performed. Chemical analysis included the amount and composition of high molecular weight (〉1 kDa) dissolved combined carbohydrates (HMW-dCCHO), particulate combined carbohydrates (pCCHO) and the carbon content of transparent exopolymer particles (TEP-C). Applied CO2 and temperature conditions were 300, 550 and 900 μatm pCO2 at 14 °C, and additionally 900 μatm pCO2 at 18 °C simulating a greenhouse ocean scenario. Enhanced nutrient stress by reducing the dilution rate (D) from D = 0.3 d−1 to D = 0.1 d−1 (D = μ) induced the strongest response in E. huxleyi. At μ = 0.3 d−1, PP was significantly higher at elevated CO2 and temperature and DO14C production correlated to PO14C production in all treatments, resulting in similar percentages of extracellular release (PER; (DO14C production/PP) × 100) averaging 3.74 ± 0.94%. At μ = 0.1 d−1, PO14C production decreased significantly, while exudation of DO14C increased. Thus, indicating a stronger partitioning from the particulate to the dissolved pool. Maximum PER of 16.3 ± 2.3% were observed at μ = 0.1 d−1 at elevated CO2 and temperature. While cell densities remained constant within each treatment and throughout the experiment, concentrations of HMW-dCCHO, pCCHO and TEP were generally higher under enhanced nutrient stress. At μ = 0.3 d−1, pCCHO concentration increased significantly with elevated CO2 and temperature. At μ = 0.1 d−1, the contribution (mol % C) of HMW-dCCHO to DOC was lower at elevated CO2 and temperature while pCCHO and TEP concentrations were higher. This was most pronounced under greenhouse conditions. Our findings suggest a stronger transformation of primary produced DOC into POC by coagulation of exudates under nutrient limitation. Our results further imply that elevated CO2 and temperature will increase exudation by E. huxleyi and may affect organic carbon partitioning in the ocean due to an enhanced transfer of HMW-dCCHO to TEP by aggregation processes.

Description: Increasing concentrations of dissolved inorganic carbon (DIC) in the interior ocean is expected as a direct consequence of increasing concentrations of CO2 in the atmosphere. This extra DIC is often referred to as anthropogenic carbon (Cant), and its inventory, or increase rate, in the interior ocean has previously been estimated by a multitude of observational approaches. Each of these methods are associated with hard to test assumptions since Cant cannot be directly observed. Results from a simpler concept with few assumptions applied to the Atlantic Ocean are reported on here using two large data collections of carbon relevant bottle data. The change in column inventory on decadal time scales, i.e. the storage rate, of DIC, respiration compensated DIC and oxygen is calculated for the Atlantic Ocean. The average storage rates for DIC and oxygen is calculated to 0.72 ± 1.22 (95% confidence interval of the mean trend: 0.65–0.78) mol m−2 yr−1 and −0.54 ± 1.64 (95% confidence interval of the mean trend: –0.64–(−0.45)) mol m−2 yr−1, respectively, for the Atlantic Ocean, where the uncertainties reflect station-to-station variability and where the mean trends are non-zero at the 95% confidence level. The standard deviation mainly reflects uncertainty due to regional variations, whereas the confidence interval reflects the mean trend. The storage rates are similar to changes found by other studies, although with large uncertainty. For the subpolar North Atlantic the storage rates show significant temporal variation of all variables. This seems to be due to variations in the prevalence of subsurface water masses with different DIC concentrations leading to sometimes different signs of storage rates for DIC and Cant. This study suggest that accurate assessment of the uptake of CO2 by the oceans will require accounting not only for processes that influence Cant but also additional processes that modify CO2 storage.

Description: We conducted measurements of the five important short-lived organic bromine species in the marine boundary layer (MBL). Measurements were made in the Northern Hemisphere mid-latitudes (Sylt Island, North Sea) in June 2009 and in the tropical Western Pacific during the TransBrom ship campaign in October 2009. For the one-week time series on Sylt Island, mean mixing ratios of CHBr3, CH2Br2, CHBr2Cl and CH2BrCl were 2.0, 1.1, 0.2, 0.1 ppt, respectively. We found maxima of 5.8 and 1.6 ppt for the two main components CHBr3 and CH2Br2. Along the cruise track in the Western Pacific (between 41° N and 13° S) we measured mean mixing ratios of 0.9, 0.9, 0.2, 0.1 and 0.1 ppt for CHBr3, CH2Br2, CHBrCl2, CHBr2Cl and CH2BrCl. Air samples with coastal influence showed considerably higher mixing ratios than the samples with open ocean origin. Correlation analyses of the two data sets yielded strong linear relationships between the mixing ratios of four of the five species (except for CH2BrCl). Using a combined data set from the two campaigns and a comparison with the results from two former studies, rough estimates of the molar emission ratios between the correlated substances were: 9/1/0.35/0.35 for CHBr3/CH2Br2/CHBrCl2/CHBr2Cl. Additional measurements were made in the tropical tropopause layer (TTL) above Teresina (Brazil, 5° S) in June 2008, using balloon-borne cryogenic whole air sampling technique. Near the level of zero clear-sky net radiative heating (LZRH) at 14.8 km about 2.25 ppt organic bromine was bound to the five short-lived species, making up 13% of total organic bromine (17.82 ppt). CH2Br2 (1.45 ppt) and CHBr3 (0.56 ppt) accounted for 90% of the budget of short-lived compounds in that region. Near the tropopause (at 17.5 km) organic bromine from these substances was reduced to 1.35 ppt, with 1.07 and 0.12 ppt attributed to CH2Br2 and CHBr3, respectively.

Description: Earth System Climate Models (ESCMs) are valuable tools that can be used to gain a better understanding of the climate system, global biogeochemical cycles and how anthropogenically-driven changes may affect them. Here we describe improvements made to the marine biogeochemical ecosystem component of the University of Victoria's ESCM (version 2.9). Major changes include corrections to the code and equations describing phytoplankton light limitation and zooplankton grazing, the implementation of a more realistic zooplankton growth and grazing model, and the implementation of an iron limitation scheme to constrain phytoplankton growth. The new model is evaluated after a 10 000-yr spin-up and compared to both the previous version and observations. For the majority of biogeochemical tracers and ecosystem processes the new model shows significant improvements when compared to the previous version and evaluated against observations. Many of the improvements are due to better simulation of seasonal changes in higher latitude ecosystems and the effect that this has on ocean biogeochemistry. This improved model is intended to provide a basic new ESCM model component, which can be used as is or expanded upon (i.e., the addition of new tracers), for climate change and biogeochemical cycling research.

Description: Lake Ohrid shared by the Republics of Albania and Macedonia is formed by a tectonically active graben within the south Balkans and suggested to be the oldest lake in Europe. Several studies have shown that the lake provides a valuable record of climatic and environmental changes and a distal tephrostratigraphic record of volcanic eruptions from Italy. Fault structures identified in seismic data demonstrate that sediments have also the potential to record tectonic activity in the region. Here, we provide an example of linking seismic and sedimentological information with tectonic activity and historical documents. Historical documents indicate that a major earthquake destroyed the city of Lychnidus (today: city of Ohrid) in the early 6th century AD. Multichannel seismic profiles, parametric sediment echosounder profiles, and a 10.08m long sediment record from the western part of the lake indicate a 2m thick mass wasting deposit, which is tentatively correlated with this earthquake. The mass wasting deposit is chronologically well constrained, as it directly overlays the AD472/AD 512 tephra. Moreover, radiocarbon dates and cross correlation with other sediment sequences with similar geochemical characteristics of the Holocene indicate that the mass wasting event took place prior to the onset of the Medieval Warm Period, and is attributed it to one of the known earthquakes in the region in the early 6th century AD.

Description: Confocal Raman microscopy (CRM) mapping was used to investigate the microstructural arrangement and organic matrix distribution within the skeleton of the coral Porites lutea. Relative changes in the crystallographic orientation of crystals within the fibrous fan-system could be mapped, without the need to prepare thin sections, as required if this information is obtained by polarized light microscopy. Simultaneously, incremental growth lines can be visualized without the necessity of etching and hence alteration of sample surface. Using these methods two types of growth lines could be identified: one corresponds to the well-known incremental growth layers, whereas the second type of growth lines resemble denticle finger-like structures (most likely traces of former spines or skeletal surfaces). We hypothesize that these lines represent the outer skeletal surface before another growth cycle of elongation, infilling and thickening of skeletal areas continues. We show that CRM mapping with high spatial resolution can significantly improve our understanding of the micro-structural arrangement and growth patterns in coral skeletons.

Description: The variability of the north-polar stratospheric vortex is a prominent aspect of the middle atmosphere. This work investigates a wide class of statistical models with respect to their ability to model geopotential and temperature anomalies, representing variability in the polar stratosphere. Four partly nonstationary, nonlinear models are assessed: linear discriminant analysis (LDA); a cluster method based on finite elements (FEM-VARX); a neural network, namely the multi-layer perceptron (MLP); and support vector regression (SVR). These methods model time series by incorporating all significant external factors simultaneously, including ENSO, QBO, the solar cycle, volcanoes, to then quantify their statistical importance. We show that variability in reanalysis data from 1980 to 2005 is successfully modeled. The period from 2005 to 2011 can be hindcasted to a certain extent, where MLP performs significantly better than the remaining models. However, variability remains that cannot be statistically hindcasted within the current framework, such as the unexpected major warming in January 2009. Finally, the statistical model with the best generalization performance is used to predict a winter 2011/12 with warm and weak vortex conditions. A vortex breakdown is predicted for late January, early February 2012.

Description: The coccolithophore Emiliania huxleyi is a marine phytoplankton species capable of forming small calcium carbonate scales (coccoliths) which cover the organic part of the cell. Calcification rates of E. huxleyi are known to be sensitive to changes in seawater carbonate chemistry. It has, however, not yet been clearly determined how these changes are reflected in size and weight of individual coccoliths and which specific parameter(s) of the carbonate system drive morphological modifications. Here, we compare data on coccolith size, weight, and malformation from a set of five experiments with a large diversity of carbonate chemistry conditions. This diversity allows distinguishing the influence of individual carbonate chemistry parameters such as carbon dioxide (CO2), bicarbonate (HCO3−), carbonate ion (CO32−), and protons (H+) on the measured parameters. Measurements of fine-scale morphological structures reveal an increase of coccolith malformation with decreasing pH suggesting that H+ is the major factor causing malformations. Coccolith distal shield area varies from about 5 to 11 μm2. Changes in size seem to be mainly induced by varying [HCO3−] and [H+] although influence of [CO32−] cannot be entirely ruled out. Changes in coccolith weight were proportional to changes in size. Increasing CaCO3 production rates are reflected in an increase in coccolith weight and an increase of the number of coccoliths formed per unit time. The combined investigation of morphological features and coccolith production rates presented in this study may help to interpret data derived from sediment cores, where coccolith morphology is used to reconstruct calcification rates in the water column.

Description: Heterocystous cyanobacteria of the genus Nodularia form extensive blooms in the Baltic Sea and contribute substantially to the total annual primary production. Moreover, they dispense a large fraction of new nitrogen to the ecosystem when inorganic nitrogen concentration in summer is low. Thus, it is of ecological importance to know how Nodularia will react to future environmental changes, in particular to increasing carbon dioxide (CO2) concentrations and what consequences there might arise for cycling of organic matter in the Baltic Sea. Here, we determined carbon (C) and dinitrogen (N2) fixation rates, growth, elemental stoichiometry of particulate organic matter and nitrogen turnover in batch cultures of the heterocystous cyanobacterium Nodularia spumigena under low (median 315 μatm), mid (median 353 μatm), and high (median 548 μatm) CO2 concentrations. Our results demonstrate an overall stimulating effect of rising pCO2 on C and N2 fixation, as well as on cell growth. An increase in pCO2 during incubation days 0 to 9 resulted in an elevation in growth rate by 84 ± 38% (low vs. high pCO2) and 40 ± 25% (mid vs. high pCO2), as well as in N2 fixation by 93 ± 35% and 38 ± 1%, respectively. C uptake rates showed high standard deviations within treatments and in between sampling days. Nevertheless, C fixation in the high pCO2 treatment was elevated compared to the other two treatments by 97% (high vs. low) and 44% (high vs. mid) at day 0 and day 3, but this effect diminished afterwards. Additionally, elevation in carbon to nitrogen and nitrogen to phosphorus ratios of the particulate biomass formed (POC : POP and PON : POP) was observed at high pCO2. Our findings suggest that rising pCO2 stimulates the growth of heterocystous diazotrophic cyanobacteria, in a similar way as reported for the non-heterocystous diazotroph Trichodesmium. Implications for biogeochemical cycling and food web dynamics, as well as ecological and socio-economical aspects in the Baltic Sea are discussed.

Description: It is expected that the calcification of foraminifera will be negatively affected by the ongoing acidification of the oceans. Compared to the open oceans, these organisms are subjected to much more adverse carbonate system conditions in coastal and estuarine environments such as the southwestern Baltic Sea, where benthic foraminifera are abundant. This study documents the seasonal changes of carbonate chemistry and the ensuing response of the foraminiferal community with bi-monthly resolution in Flensburg Fjord. In comparison to the surface pCO2, which is close to equilibrium with the atmosphere, we observed large seasonal fluctuations of pCO2 in the bottom and sediment pore waters. The sediment pore water pCO2 was constantly high during the entire year ranging from 1244 to 3324 μatm. Nevertheless, in contrast to the bottom water, sediment pore water was slightly supersaturated with respect to calcite as consequence of higher alkalinity (AT) for the most time of the year. Foraminiferal assemblages were dominated by two calcareous species, Ammonia aomoriensis and Elphidium incertum, and the agglutinated Ammotium cassis. The one year-cycle was characterized by seasonal community shifts. Our results revealed that there is no dynamic response of foraminiferal population density and diversity to elevated sediment pore water pCO2. Surprisingly, the fluctuations of sediment pore water undersaturation (Ωcalc) co-vary with the population densities of living Ammonia aomoriensis. Further, we observed that most of the tests of living calcifying specimens were intact. Only Ammonia aomorienis showed dissolution and recalcification structures on the tests, especially at undersaturated conditions. Therefore, the benthic community is subjected to constantly high pCO2 and tolerates elevated levels as long as sediment pore water remains supersaturated. Model calculations inferred that increasing atmospheric CO2 concentrations will finally lead to a perennial undersaturation in sediment pore waters. Whereas benthic foraminifera indeed may cope with a high sediment pore water pCO2, the steady undersaturation of sediment pore waters would likely cause a significant higher mortality of the dominating Ammonia aomoriensis. This shift may eventually lead to changes in the benthic foraminiferal communities in Flensburg Fjord, as well as in other regions experiencing naturally undersaturated Ωcalc levels.

Description: The Eastern Tropical Pacific (ETP) is believed to be one of the largest marine sources of the greenhouse gas nitrous oxide N2O). Future N2Oemissions from the ETP are highly uncertain because oxygen minimum zones are expected to expand, affecting both regional production and consumption of N2O. Here we assess three primary uncertainties in how N2O may respond to changing O2 levels: (1) the relationship between N2O production and O2 (is it linear or exponential at low O2 concentrations?), (2) the cutoff point at which net N2O production switches to net N2O consumption (uncertainties in this parameterization can lead to differences in model ETP N2O concentrations of more than 20%), and (3) the rate of net N2O consumption at low O2. Based on the MEMENTO database, which is the largest N2O dataset currently available, we find that N2O production in the ETP increases linearly rather than exponentially with decreasing O2. Additionally, net N2O consumption switches to net N2O production at ~ 10 μM O2, a value in line with recent studies that suggest consumption occurs on a larger scale than previously thought. N2O consumption is on the order of 0.129 mmol N2O m−3 yr−1 in the Peru–Chile Undercurrent. Based on these findings, it appears that recent studies substantially overestimated N2O production in the ETP. In light of expected deoxygenation, future N2O production is still uncertain, but due to higher-than-expected consumption levels, it is possible that N2Oconcentrations may decrease rather than increase as oxygen minimum zones expand.

Description: Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island. Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

Description: Coccolithophores, a key phytoplankton group, are one of the most studied organisms regarding their physiological response to ocean acidification/carbonation. The biogenic production of calcareous coccoliths has made coccolithophores a promising group for paleoceanographic research aiming to reconstruct past environmental conditions. Recently, geochemical and morphological analyses of fossil coccoliths have gained increased interest in regard to changes in seawater carbonate chemistry. The cosmopolitan coccolithophore Emiliania huxleyi (Lohm.) Hay and Mohler was cultured over a range of pCO2 levels in controlled laboratory experiments under nutrient replete and nitrogen limited conditions. Measurements of photosynthesis and calcification revealed, as previously published, an increase in particulate organic carbon production and a moderate decrease in calcification from ambient to elevated pCO2. The enhancement in particulate organic carbon production was accompanied by an increase in cell diameter. Changes in coccolith volume were best correlated with the coccosphere/cell diameter and no significant correlation was found between the coccolith volume and the particulate inorganic carbon production. The conducted experiments revealed that the coccolith volume of E. huxleyi is variable with aquatic CO2 concentration but its sensitivity is rather small in comparison with its sensitivity to nitrogen limitation. Comparing coccolith morphological and geometrical parameters like volume, mass and size to physiological parameters under controlled laboratory conditions is an important step to understand variations in fossil coccolith geometry.

Description: Fixed nitrogen (N) loss to biogenic N2 in intense oceanic O2 minimum zones (OMZ) accounts for a large fraction of the global N sink and is an essential control on the ocean's N budget. However, major uncertainties exist regarding microbial pathways as well as net impact on the magnitude of N-loss and the ocean's overall N budget. Here we report the discovery of a N-loss hotspot in the Peru OMZ associated with a coastally trapped mesoscale eddy that is marked by an extreme N deficit matched by biogenic N2 production, high NO2− levels, and the highest isotope enrichments observed so far in OMZ's for the residual NO3−. High sea surface chlorophyll (SSC) in seaward flowing streamers provides evidence for offshore eddy transport of highly productive, inshore water. Resulting pulses in the downward flux of particles likely stimulated heterotrophic dissimilatory NO3− reduction and subsequent production of biogenic N2. The associated temporal/spatial heterogeneity of N-loss, mediated by a local succession of microbial processes, may explain inconsistencies observed among prior studies. Similar transient enhancements of N-loss likely occur within all other major OMZ's exerting a major influence on global ocean N and N isotope budgets.

Description: Dimethylsulphide (DMS) and dissolved and particulate dimethylsulfoniopropionate (DMSPd, DMSPp) were measured in near-surface waters along theMauritanian coast, Northwest Africa, during the upwelling season in February 2008. DMS, DMSPd and DMSPp surface concentrations of up to 10 nmol L−1, 15 nmol L−1 and 990 nmol L−1, respectively, were measured. However, the DMS concentrations measured are in the low range compared to other upwelling regions. The maximum DMSPp concentration is the highest reported from upwelling regions so far, which might indicate that the Mauritanian upwelling is a hot spot for DMSP. Within the phytoplankton groups, dinoflagellates were identified as important contributors to DMS concentrations, while other algae seemed to have only a minor or no influence on DMS and DMSP concentrations. A pronounced switch from high DMSP to high DMS concentrations was observed when the nitrogen to phosphorus ratio (N:P) was below 7. The high DMS/DMSP ratios at N:P ratios 〈7 indicate that nitrogen limitation presumably triggered a switch from DMSP to DMS independent of the species composition. Our results underline the importance of coastal upwelling regions as a local source for surface seawater sulphur.

Description: Within Europe there are more than 380 Ocean Bottom Seismometers (OBS) distributed across 10 instrument parks in 6 countries. At least 120 of these OBS are wideband or broadband, over 260 can be deployed for at least 6 months at a time and 140 for at least one year. New parks are planned in two other European countries, which should add over 70 OBSs to this “fleet”. However, these parks are under the control of individual countries or universities and hence to date this has made it difficult to organize large-scale experiments, especially for seismologists without marine experience. There has recently been an initiative to coordinate the use of these distributed instruments and their data products, to encourage large-scale experiments, possibly with onshore and offshore components, by seismologists who have not necessarily used OBSs before. The ongoing or planned developments include: Helping scientists with marine-specific formalities such as ship requests; clearer explanations of the noise floors of OBS instrumentation; improved clarity of instrument pricing and availability; standardized data output formats and data validation; and archiving in established seismological data centers. These efforts should allow improved experiment design in scientifically interesting regions with an offshore component and an easier, clearer way to organize large-scale, multi-country experiments. We will present details of this initiative to help organize large-scale experiments, the particularities of OBS sensors and marine deployments, the available instrumentation and new developments.

Description: The recent finding that microbial ammonia oxidation in the ocean is performed by archaea to a greater extent than by bacteria has drastically changed the view on oceanic nitrification. The numerical dominance of archaeal ammonia-oxidizers (AOA) over their bacterial counterparts (AOB) in large parts of the ocean leads to the hypothesis that AOA rather than AOB could be the key organisms for the oceanic production of the strong greenhouse gas nitrous oxide (N2O) that occurs as a by-product of nitrification. Very recently, enrichment cultures of marine ammonia-oxidizing archaea have been reported to produce N2O. Here, we demonstrate that archaeal ammonia monooxygenase genes (amoA) were detectable throughout the water column of the eastern tropical North Atlantic (ETNA) and eastern tropical South Pacific (ETSP) Oceans. Particularly in the ETNA, comparable patterns of abundance and expression of archaeal amoA genes and N2O co-occurred in the oxygen minimum, whereas the abundances of bacterial amoA genes were negligible. Moreover, selective inhibition of archaea in seawater incubations from the ETNA decreased the N2O production significantly. In studies with the only cultivated marine archaeal ammonia-oxidizer Nitrosopumilus maritimus SCM1, we provide the first direct evidence for N2O production in a pure culture of AOA, excluding the involvement of other microorganisms as possibly present in enrichments. N. maritimus showed high N2O production rates under low oxygen concentrations comparable to concentrations existing in the oxycline of the ETNA, whereas the N2O production from two AOB cultures was comparably low under similar conditions. Based on our findings, we hypothesize that the production of N2O in tropical ocean areas results mainly from archaeal nitrification and will be affected by the predicted decrease in dissolved oxygen in the ocean.

Description: A submarine eruption started off the south coast of El Hierro, Canary Islands, on 10 October 2011 and continues at the time of this writing (February 2012). In the first days of the event, peculiar eruption products were found floating on the sea surface, drifting for long distances from the eruption site. These specimens, which have in the meantime been termed "restingolites" (after the close-by village of La Restinga), appeared as black volcanic "bombs" that exhibit cores of white and porous pumice-like material. Since their brief appearance, the nature and origin of these "floating stones" has been vigorously debated among researchers, with important implications for the interpretation of the hazard potential of the ongoing eruption. The "restingolites" have been proposed to be either (i) juvenile high-silica magma (e.g. rhyolite), (ii) remelted magmatic material (trachyte), (iii) altered volcanic rock, or (iv) reheated hyaloclastites or zeolite from the submarine slopes of El Hierro. Here, we provide evidence that supports yet a different conclusion. We have analysed the textures and compositions of representative "restingolites" and compared the results to previous work on similar rocks found in the Canary Islands. Based on their high-silica content, the lack of igneous trace element signatures, the presence of remnant quartz crystals, jasper fragments and carbonate as well as wollastonite (derived from thermal overprint of carbonate) and their relatively high oxygen isotope values, we conclude that "restingolites" are in fact xenoliths from pre-island sedimentary layers that were picked up and heated by the ascending magma, causing them to partially melt and vesiculate. As they are closely resembling pumice in appearance, but are xenolithic in origin, we refer to these rocks as "xeno-pumice". The El Hierro xeno-pumices hence represent messengers from depth that help us to understand the interaction between ascending magma and crustal lithologies beneath the Canary Islands as well as in similar Atlantic islands that rest on sediment-covered ocean crust (e.g. Cape Verdes, Azores). The occurrence of "restingolites" indicates that crustal recycling is a relevant process in ocean islands, too, but does not herald the arrival of potentially explosive high-silica magma in the active plumbing system beneath El Hierro.

Description: A Monte Carlo based radiative transfer model has been developed for calculating the availability of solar radiation within the top 100 m of the ocean. The model is optimized for simulations of spatial high resolution downwelling irradiance Ed fluctuations that arise from the lensing effect of waves at the water surface. In a first step the accuracy of simulation results have been verified by measurements of the oceanic underwater light field and through intercomparison with an established radiative transfer model. Secondly the potential depth-impact of nonlinear shaped single waves, from capillary to swell waves, is assessed by considering the most favorable conditions for light focusing, i.e. monochromatic light at 490 nm, very clear oceanic water with a low chlorophyll a content of 0.1 mg m−3 and high sun elevation. Finally light fields below irregular wave profiles accounting for realistic sea states were simulated. Our simulations suggest that under open ocean conditions light flashes with 50 % irradiance enhancements can appear down to 35 m depth, and light variability in the range of ±10 % compared to the mean Ed is still possible in 100 m depth.

Description: Phosphate distributions simulated by seven state-of-the-art biogeochemical ocean circulation models are evaluated against observations of global ocean nutrient distributions. The biogeochemical models exhibit different structural complexities, ranging from simple nutrient-restoring to multi-nutrient NPZD type models. We evaluate the simulations using the observed volume distribution of phosphate. The errors in these simulated volume class distributions are significantly larger when preformed phosphate (or regenerated phosphate) rather than total phosphate is considered. Our analysis reveals that models can achieve similarly good fits to observed total phosphate distributions for a very different partitioning into preformed and regenerated nutrient components. This has implications for the strength and potential climate sensitivity of the simulated biological carbon pump. We suggest complementing the use of total nutrient distributions for assessing model skill by an evaluation of the respective preformed and regenerated nutrient components.

Description: Ocean Drilling Program (ODP) Site 982 provided a key sediment section at Rockall Plateau for reconstructing northeast Atlantic paleoceanography and monitoring benthic δ18O stratigraphy over the late Pliocene to Quaternary onset of major Northern Hemisphere glaciation. A renewed hole-specific inspection of magnetostratigraphic reversals and the addition of epibenthic δ18O records for short Pliocene sections in holes 982A, B, and C, crossing core breaks in the δ18O record published for Hole 982B, now imply a major revision of composite core depths. After tuning to the orbitally tuned reference record LR04, the new composite δ18O record results in a hiatus, where the Kaena magnetic subchron might have been lost, and in a significant age reduction for all proxy records by 130 to 20 ky over the time span 3.2–2.7 million years ago (Ma). Our study demonstrates the general significance of reliable composite-depth scales and δ18O stratigraphies in ODP sediment records for generating ocean-wide correlations in paleoceanography. The new concept of age control makes the late Pliocene trends in SST (sea surface temperature) and atmospheric pCO2 at Site 982 more consistent with various paleoclimate trends published from elsewhere in the North Atlantic.

Description: Benthic foraminifera have proven to be suitable for environmental monitoring because of their high levels of adaptation, small size and high abundance in Recent sediments and the fossil record. Foraminifera are scarcely used in monitoring studies because a standardization of methods has not been achieved to date. When particular methods were introduced and why they were applied is often hidden in the literature. This paper reviews the development of field and laboratory methods, their constraints and consequences for faunal and data analyses. Multiple and box corers and some grab samplers retrieve reliable surface sediment samples provided the bow wave is minimized as the sampler approaches the sea floor. Most disturbances are created during handling of the unit on deck and subsampling. Ethanol for preservation, rose Bengal as vital stain and a mesh size of 63 µm to wash foraminiferal samples are used extensively. Faunal analyses of a larger size fraction are occasionally necessary. The fractions 〉125 µm and 〉150 µm are often preferentially chosen even though this may artificially reduce specimen numbers and faunal diversity. Generally, a much lower level of common practice prevails in sample preparation and faunal analyses than in sampling or laboratory procedures. Increasing preference has been given to quantitative methods and the acquisition of independently revisable census data during recent decades.

Description: Sea-to-air and diapycnal fluxes of nitrous oxide (N2O) into the mixed layer were determined during three cruises to the upwelling region off Mauritania. Sea-to-air fluxes as well as diapycnal fluxes were elevated close to the shelf break, but elevated sea-to-air fluxes reached further offshore as a result of the offshore transport of upwelled water masses. To calculate a mixed layer budget for N2O we compared the regionally averaged sea-to-air and diapycnal fluxes and estimated the potential contribution of other processes, such as vertical advection and biological N2O production in the mixed layer. Using common parameterizations for the gas transfer velocity, the comparison of the average sea-toair and diapycnal N2O fluxes indicated that the mean sea-toair flux is about three to four times larger than the diapycnal flux. Neither vertical and horizontal advection nor biological production were found sufficient to close the mixed layer budget. Instead, the sea-to-air flux, calculated using a parameterization that takes into account the attenuating effect of surfactants on gas exchange, is in the same range as the diapycnal flux. From our observations we conclude that common parameterizations for the gas transfer velocity likely overestimate the air-sea gas exchange within highly productive upwelling zones.

Description: The ongoing rise in atmospheric pCO2 and consequent increase in ocean acidification have direct effects on marine calcifying phytoplankton, which potentially alters carbon export. To date it remains unclear, firstly, how nutrient regime, in particular by coccolithophores preferred phosphate limitation, interacts with pCO2 on particulate carbon accumulation; secondly, how direct physiological responses on the cellular level translate into total population response. In this study, cultures of Emiliania huxleyi were full-factorially exposed to two different N:P regimes and three different pCO2 levels. Cellular biovolume and PIC and POC content significantly declined in response to pCO2 in both nutrient regimes. Cellular PON content significantly increased in the Redfield treatment and decreased in the high N:P regime. Cell abundance significantly declined in the Redfield and remained constant in the high N:P regime. We hypothesise that in the high N:P regime severe phosphorous limitation could be compensated either by reduced inorganic phosphorous demand and/or by enzymatic uptake of organic phosphorous. In the Redfield regime we suggest that enzymatic phosphorous uptake to supplement enhanced phosphorous demand with pCO2 was not possible and thus cell abundance declined. These hypothesised different physiological responses of E. huxleyi among the nutrient regimes significantly altered population carrying capacities along the pCO2 gradient. This ultimately led to the attenuated total population response in POC and PIC content and biovolume to increased pCO2 in the high N:P regime. Our results point to the fact that the physiological (i.e. cellular) PIC and POC response to ocean acidification cannot be linearly extrapolated to total population response and thus carbon export. It is therefore necessary to consider both effects of nutrient limitation on cell physiology and their consequences for population size when predicting the influence of coccolithophores on atmospheric pCO2 feedback and their function in carbon export mechanisms.

Description: Increasing concentrations of atmospheric carbon dioxide are projected to lead to an increase in sea surface temperatures, potentially impacting marine ecosystems and biogeochemical cycling. Here we conducted an indoor mesocosm experiment with a natural plankton community taken from the Baltic Sea in summer. We induced a plankton bloom via nutrient addition and followed the dynamics of the different carbon and nitrogen pools for a period of one month at temperatures ranging from 9.5 °C to 17.5 °C, representing a range of ± 4 °C relative to ambient temperature. The uptake of dissolved inorganic carbon (DIC) and the net build-up of both particulate (POC) and dissolved organic carbon (DOC) were all enhanced at higher temperatures and almost doubled over a temperature gradient of 8 °C. Furthermore, elemental ratios of carbon and nitrogen (C:N) in both particulate and dissolved organic matter increased in response to higher temperatures, both reaching very high C:N ratios of 〉30 at +4 °C. Altogether, these observations suggest a pronounced increase in excess carbon fixation in response to elevated temperatures. Most of these findings are contrary to results from similar experiments conducted with plankton populations sampled in spring, revealing large uncertainties in our knowledge of temperature sensitivities of key processes in marine carbon cycling. Since a major difference to previous mesocosm experiments was the dominant phytoplankton species, we hypothesize that species composition might play an important role in the response of biogeochemical cycling to increasing temperatures.

Description: Comprehensive synoptic datasets (surface water down to 4000 m) of dissolved cadmium (Cd), copper (Cu), manganese (Mn), lead (Pb) and silver (Ag) are presented along a section between 34° S and 57° S in the southeastern Atlantic Ocean and the Southern Ocean to the south off South Africa. The vertical distributions of Cu and Ag display nutrient-like profiles similar to silicic acid, and of Cd similar to phosphate. The distribution of Mn shows a subsurface maximum in the oxygen minimum zone, whereas Pb concentrations are rather invariable with depth. Dry deposition of aerosols is thought to be an important source of Pb to surface waters close to South Africa, and dry deposition and snowfall may have been significant sources of Cu and Mn at the higher latitudes. Furthermore, the advection of water masses enriched in trace metals following contact with continental margins appeared to be an important source of trace elements to the surface, intermediate and deep waters in the southeastern Atlantic Ocean and the Antarctic Circumpolar Current. Hydrothermal inputs may have formed a source of trace metals to the deep waters over the Bouvet Triple Junction ridge crest, as suggested by relatively enhanced dissolved Mn concentrations. The biological utilization of Cu and Ag was proportional to that of silicic acid across the section, suggesting that diatoms formed an important control over the removal of Cu and Ag from surface waters. However, uptake by dino- and nano-flagellates may have influenced the distribution of Cu and Ag in the surface waters of the subtropical Atlantic domain. Cadmium correlated strongly with phosphate (P), yielding lower Cd / P ratios in the subtropical surface waters where phosphate concentrations were below 0.95 μM. The greater depletion of Cd relative to P observed in the Weddell Gyre compared to the Antarctic Circumpolar Current could be due to increase Cd uptake induced by iron-limiting conditions in these high-nutrient–low-chlorophyll waters. Similarly, an increase of Mn uptake under Fe-depleted conditions may have caused the highest depletion of Mn relative to P in the surface waters of the Weddell Gyre. In addition, a cellular Mn-transport channel of Cd was possibly activated in the Weddell Gyre, which in turn may have yielded depletion of both Mn and Cd in these surface waters.

Description: Marine N2 fixing microorganisms, termed diazotrophs, are a key functional group in marine pelagic ecosystems. The biological fixation of dinitrogen (N2) to bioavailable nitrogen provides an important new source of nitrogen for pelagic marine ecosystems and influences primary productivity and organic matter export to the deep ocean. As one of a series of efforts to collect biomass and rates specific to different phytoplankton functional groups, we have constructed a database on diazotrophic organisms in the global pelagic upper ocean by compiling about 12 000 direct field measurements of cyanobacterial diazotroph abundances (based on microscopic cell counts or qPCR assays targeting the nifH genes) and N2 fixation rates. Biomass conversion factors are estimated based on cell sizes to convert abundance data to diazotrophic biomass. The database is limited spatially, lacking large regions of the ocean especially in the Indian Ocean. The data are approximately log-normal distributed, and large variances exist in most sub-databases with non-zero values differing 5 to 8 orders of magnitude. Reporting the geometric mean and the range of one geometric standard error below and above the geometric mean, the pelagic N2 fixation rate in the global ocean is estimated to be 62 (52–73) Tg N yr−1 and the pelagic diazotrophic biomass in the global ocean is estimated to be 2.1 (1.4–3.1) Tg C from cell counts and to 89 (43–150) Tg C from nifH-based abundances. Reporting the arithmetic mean and one standard error instead, these three global estimates are 140 ± 9.2 Tg N yr−1, 18 ± 1.8 Tg C and 590 ± 70 Tg C, respectively. Uncertainties related to biomass conversion factors can change the estimate of geometric mean pelagic diazotrophic biomass in the global ocean by about ±70%. It was recently established that the most commonly applied method used to measure N2 fixation has underestimated the true rates. As a result, one can expect that future rate measurements will shift the mean N2 fixation rate upward and may result in significantly higher estimates for the global N2 fixation. The evolving database can nevertheless be used to study spatial and temporal distributions and variations of marine N2 fixation, to validate geochemical estimates and to parameterize and validate biogeochemical models, keeping in mind that future rate measurements may rise in the future. The database is stored in PANGAEA (doi:10.1594/PANGAEA.774851).