ALBERT

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

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

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

Description: The Mediterranean Sea is a semi-enclosed sea characterized by high salinities, temperatures and densities. The net evaporation exceeds the precipitation, driving an anti-estuarine circulation through the Strait of Gibraltar, contributing to very low nutrient concentrations. The Mediterranean Sea has an active overturning circulation, one shallow cell that communicates directly with the Atlantic Ocean, and two deep overturning cells, one in each of the two main basins. It is surrounded by populated areas and is thus sensitive to anthropogenic forcing. Several dramatic changes in the oceanographic and biogeochemical conditions have been observed during the past several decades, emphasizing the need to better monitor and understand the changing conditions and their drivers. During 2011 three oceanographic cruises were conducted in a coordinated fashion in order to produce baseline data of important physical and biogeochemical parameters that can be compared to historic data and be used as reference for future observational campaigns. In this article we provide information on the Mediterranean Sea oceanographic situation, and present a short review that will serve as background information for the special issue in Ocean Science on "Physical, chemical and biological oceanography of the Mediterranean Sea". An important contribution of this article is the set of figures showing the large-scale distributions of physical and chemical properties along the full length

Description: Recent studies on the impacts of ocean acidification on pelagic communities have identified changes in carbon to nutrient dynamics with related shifts in elemental stoichiometry. In principle, mesocosm experiments provide the opportunity of determining temporal dynamics of all relevant carbon and nutrient pools and, thus, calculating elemental budgets. In practice, attempts to budget mesocosm enclosures are often hampered by uncertainties in some of the measured pools and fluxes, in particular due to uncertainties in constraining air–sea gas exchange, particle sinking, and wall growth. In an Arctic mesocosm study on ocean acidification applying KOSMOS (Kiel Off-Shore Mesocosms for future Ocean Simulation), all relevant element pools and fluxes of carbon, nitrogen and phosphorus were measured, using an improved experimental design intended to narrow down the mentioned uncertainties. Water-column concentrations of particulate and dissolved organic and inorganic matter were determined daily. New approaches for quantitative estimates of material sinking to the bottom of the mesocosms and gas exchange in 48 h temporal resolution as well as estimates of wall growth were developed to close the gaps in element budgets. However, losses elements from the budgets into a sum of insufficiently determined pools were detected, and are principally unavoidable in mesocosm investigation. The comparison of variability patterns of all single measured datasets revealed analytic precision to be the main issue in determination of budgets. Uncertainties in dissolved organic carbon (DOC), nitrogen (DON) and particulate organic phosphorus (POP) were much higher than the summed error in determination of the same elements in all other pools. With estimates provided for all other major elemental pools, mass balance calculations could be used to infer the temporal development of DOC, DON and POP pools. Future elevated pCO2 was found to enhance net autotrophic community carbon uptake in two of the three experimental phases but did not significantly affect particle elemental composition. Enhanced carbon consumption appears to result in accumulation of dissolved organic carbon under nutrient-recycling summer conditions. This carbon over-consumption effect becomes evident from mass balance calculations, but was too small to be resolved by direct measurements of dissolved organic matter. Faster nutrient uptake by comparatively small algae at high CO2 after nutrient addition resulted in reduced production rates under future ocean CO2 conditions at the end of the experiment. This CO2 mediated shift towards smaller phytoplankton and enhanced cycling of dissolved matter restricted the development of larger phytoplankton, thus pushing the system towards a retention type food chain with overall negative effects on export potential.

Description: Here we report on data from an oceanographic cruise on the German research vessel Meteor covering large parts of the Mediterranean Sea during spring of 2011. The main objectives of this cruise was to conduct measurements of physical, chemical and biological variables on a section across the Mediterranean Sea with the goal of producing a synoptic picture of the distribution of relevant physical and biogeochemical properties, in order to compare those to historic data sets. During the cruise, a comprehensive data set of relevant variables following the guide lines for repeat hydrography outlined by the GO-SHIP group (http://www.go-ship.org/) was collected. The measurements include; salinity and temperature (CTD), an over-determined carbonate system, inorganic nutrients, oxygen, transient tracers (CFC-12, SF6), Helium isotopes and tritium, and carbon isotopes. The cruise sampled all major basins of the Mediterranean Sea following roughly an east-to-west section from the coast of Lebanon to through the Strait of Gibraltar, and to the coast of Portugal. Also a south-to-north section from the Ionian Sea to the Adriatic Sea was carried out. Additionally, sampling in the Aegean, Adriatic and Tyrrhenian Seas were carried out. The sections roughly followed lines and positions that have been sampled previously during other programs, thus providing the opportunity for comparative investigations of the temporal development of various parameters.

Description: The oceanic biological carbon pump is an important factor in the global carbon cycle. Organic carbon is exported from the surface ocean mainly in the form of settling particles derived from plankton production in the upper layers of the ocean. The large variability in current estimates of the global strength of the biological carbon pump emphasises that our knowledge of a major planetary carbon flux remains poorly constrained. We present a database of 723 estimates of organic carbon export from the surface ocean derived from the 234Th technique. The dataset is archived on the data repository PANGEA® (www.pangea.de) under doi:10.1594/PANGAEA.809717. Data were collected from tables in papers published between 1985 and early 2013. We also present sampling dates, publication dates and sampling areas. Most of the open ocean provinces are represented by multiple measurements. However, the western Pacific, the Atlantic Arctic, South Pacific and the southern Indian Ocean are not well represented. There is a variety of integration depths ranging from surface to 300 m. Globally the fluxes ranged from 0 to 1500 mg C m−2 d−1.

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

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

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

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

Description: The size of the bio-available (i.e. "fixed") nitrogen inventory in the ocean influences global marine productivity and the biological carbon pump. Despite its importance, the pre-industrial rates for the major source and sink terms of the oceanic fixed nitrogen budget, N2 fixation and denitrification, respectively, are not well known. However, these processes leave distinguishable imprints on the ratio of stable nitrogen isotopes, δ15N, which can therefore help to infer their patterns and rates. Here we use δ15N observations from the water column and a new database of seafloor measurements to constrain rates of N2 fixation and denitrification predicted by a global three-dimensional Model of Ocean Biogeochemistry and Isotopes (MOBI). Sensitivity experiments were performed to quantify uncertainties associated with the isotope effect of denitrification in the water column and sediments. They show that the level of nitrate utilization in suboxic zones, that is the balance between nitrate consumption by denitrification and nitrate replenishment by mixing (dilution effect), significantly affects the isotope effect of water column denitrification and thus global mean δ15NO3−. Experiments with lower levels of nitrate utilization within the suboxic zone (i.e. higher residual water column nitrate concentrations, ranging from 20–32 μM) require higher ratios of benthic to water column denitrification (BD:WCD = 0.75–1.4, respectively), to satisfy the global mean NO3− and δ15NO3− constraints in the modern ocean. This suggests that nitrate utilization in suboxic zones play an important role in global nitrogen isotope cycling. Increasing the net fractionation factor for benthic denitrification (ϵBD = 0–4‰) requires even higher ratios of benthic to water column denitrification (BD:WCD = 1.4–3.5, respectively). The model experiments that best reproduce observed seafloor δ15N support the middle to high-end estimates for the net fractionation factor of benthic denitrification (ϵBD = 2–4‰). Assuming a balanced fixed nitrogen budget, we estimate that pre-industrial rates of N2 fixation, water column denitrification, and benthic denitrification were approximately 195–345, 65–75, and 130–270 Tg N yr−1, respectively. Although uncertainties still exist, these results suggest that previous estimates of N2 fixation have been significantly underestimated and the residence time for oceanic fixed nitrogen is between ~ 1500–3000 yr.

Description: We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements from three tropical ship campaigns and the Lagrangian transport model FLEXPART, we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I troposphere–stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere)-Sonne research vessel campaign in the coastal western Pacific. The other two campaigns give considerably smaller maxima of 0.1 ppt CH3I in the open western Pacific and 0.03 ppt in the coastal eastern Atlantic. In order to assess the representativeness of the large local mixing ratios, we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared with available upper air measurements, including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the eastern Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement, indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical regions that are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the western Pacific. Overall our model results give a tropical contribution of 0.04 ppt CH3I to the stratospheric iodine budget. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine.

Description: Methyl iodide (CH3I) is a volatile organic halogen compound that contributes significantly to the transport of iodine from the ocean to the atmosphere, where it plays an important role in tropospheric chemistry. CH3I is naturally produced and occurs in the global ocean. The processes involved in the formation of CH3I, however, are not fully understood. In fact, there is an ongoing debate whether production by phytoplankton or photochemical degradation of organic matter is the main source term. Here, both the biological and photochemical production mechanisms are considered in a biogeochemical module that is coupled to a one-dimensional water column model for the eastern tropical Atlantic. The model is able to reproduce observed subsurface maxima of CH3I concentrations. But, the dominating source process cannot be clearly identified as subsurface maxima can occur due to both direct biological and photochemical production. However, good agreement between the observed and simulated difference between surface and subsurface methyl iodide concentrations is achieved only when direct biological production is taken into account. Production rates for the biological CH3I source that were derived from published laboratory studies are shown to be inappropriate for explaining CH3I concentrations in the eastern tropical Atlantic.

Description: The Gulf of Cadiz is an extensive seepage area in the south Iberian margin (NE Atlantic) encompassing over 40 mud volcanoes (MVs) at depths ranging from 200 to 4000 m. The area has a long geologic history and a central biogeographic location with a complex circulation ensuring oceanographic connectivity with the Mediterranean Sea, equatorial and North Atlantic regions. The geodynamics of the region promotes a notorious diversity in the seep regime despite the relatively low fluxes of hydrocarbon-rich gases. We analyse quantitative samples taken during the cruises TTR14, TTR15 and MSM01-03 in seven mud volcanoes grouped into Shallow MVs (Mercator: 350 m, Kidd: 500 m, Meknes: 700 m) and Deep MVs (Captain Arutyunov: 1300 m, Carlos Ribeiro: 2200 m, Bonjardim: 3000 m, Porto: 3900 m) and two additional Reference sites (ca. 550 m). Macrofauna (retained by a 500 mu m sieve) was identified to species level whenever possible. The samples yielded modest abundances (70-1567 individuals per 0.25m(2)), but the local and regional number of species is among the highest ever reported for cold seeps. Among the 366 recorded species, 22 were symbiont-hosting bivalves (Thyasiridae, Vesicomyidae, Solemyidae) and tubeworms (Siboglinidae). The multivariate analyses supported the significant differences between Shallow and Deep MVs: The environmental conditions at the Shallow MVs make them highly permeable to the penetration of background fauna leading to high diversity of the attendant assemblages (H': 2.92-3.94; ES(100): 28.3-45.0; J': 0.685-0.881). The Deep MV assemblages showed, in general, contrasting features but were more heterogeneous (H': 1.41-3.06; ES(100): 10.5-30.5; J': 0.340-0.852) and often dominated by one or more siboglinid species. The rarefaction curves confirmed the differences in biodiversity of Deep and Shallow MVs as well as the convergence of the latter to the Reference sites. The Bray-Curtis dissimilarity demonstrated the high beta-diversity of the assemblages, especially in pairwise comparisons involving samples from the Deep MVs. Diversity partitioning assessed for species richness, Hurlbert's expected number of species and Shannon-Wiener index confirmed the high beta-diversity across different spatial scales (within MVs, between MVs, between Deep and Shallow MVs). We suggest that historical and contemporary factors with differential synergies at different depths contribute to the high alpha-, beta- and gamma-diversity of the mud volcano faunal assemblages in the Gulf of Cadiz.

Description: Despite the worldwide occurrence of marine hypoxic regions, benthic nitrogen (N) cycling within these areas is poorly understood and it is generally assumed that these areas represent zones of intense fixed N loss from the marine system. Sulfate reduction can be an important process for organic matter degradation in sediments beneath hypoxic waters and many sulfate-reducing bacteria (SRB) have the genetic potential to fix molecular N (N2). Therefore, SRB may supply fixed N to these systems, countering some of the N lost via microbial processes such as denitrification and anaerobic ammonium oxidation. The objective of this study was to evaluate if N2-fixation, possibly by SRB, plays a role in N cycling within the seasonally hypoxic sediments from Eckernförde Bay, Baltic Sea. Monthly samplings were performed over the course of one year to measure N2-fixation and sulfate reduction rates, to determine the seasonal variations in bioturbation (bioirrigation) activity and important benthic geochemical profiles, such as sulfur and N compounds, and to monitor changes in water column temperature and oxygen concentrations. Additionally, at several time points, rates of benthic denitrification were also measured and the active N-fixing community was examined via molecular tools. Integrated rates of N2-fixation and sulfate reduction showed a similar seasonality pattern, with highest rates occurring in August (approx. 22 and 880 nmol cm−3 d−1 of N and SO42−, respectively) and October (approx. 22 and 1300 nmol cm−3 d−1 of N and SO42−, respectively), and lowest rates occurring in February (approx. 8 and 32 nmol cm−3 d−1 of N and SO42−, respectively). These rate changes were positively correlated with bottom water temperatures and previous reported plankton bloom activities, and negatively correlated with bottom water oxygen concentrations. Other variables that also appeared to play a role in rate determination were bioturbation, bubble irrigation and winter storm events. Molecular analysis demonstrated the presence of nifH sequences related to two known N2-fixing SRB, namely Desulfovibrio vulgaris and Desulfonema limicola, supporting the hypothesis that some of the nitrogenase activity detected may be attributed to SRB. Denitrification appeared to follow a similar trend as the other microbial processes and the ratio of denitrification to N2-fixation ranged from 6.8 in August to 1.1 in February, indicating that in February, the two processes are close to being in balance in terms of N loss and N gain. Overall, our data show that Eckernförde Bay represents a complex ecosystem where numerous environmental variables combine to influence benthic microbial activities involving N and sulfur cycling.

Description: The impact of ocean acidification and carbonation on microbial community structure was assessed during a large-scale in situ costal pelagic mesocosm study, included as part of the EPOCA 2010 Arctic campaign. The mesocosm experiment included ambient conditions (fjord) and nine mesocosms, with pCO2 range from ~145 to ~1420 μatm. Samples collected at nine time points (t-1, t1, t5, t7, t12, t14, t22, t26 to t28) in seven treatments (ambient fjord (~145), 2×~185, ~270, ~685, ~820, ~1050 μatm) were analysed for "free-living" and "particle associated" microbial community composition using 16S rRNA amplicon sequencing. This high-throughput sequencing analysis produced ~20 000 000 16S rRNA V4 reads, which comprised 7000 OTUs. The main variables structuring these communities were, sample origin (fjord or mesocosms) and the filter size fraction (free-living or particle associated). The community was significantly different between the fjord and both the control and elevated 2 mesocosms (which were not significant different) after nutrients were added to the mesocosms; suggesting that the addition of nutrients is the primary driver of the change in mesocosm community structure. The relative importance of each structuring variable depended greatly on the time at which the community was sampled in relation to the phytoplankton bloom. The size fraction was the second most important factor for community structure; separating free-living from particle-associated bacteria. When free-living and particle-associated bacteria were analysed separately at different time points, the only taxon pCO2 was found to significantly affect were the Gammaproteobacteria after nutrient addition. Finally, pCO2 treatment was found to be significantly correlated (non-linear) with 15 rare taxa, most of which increased in abundance with higher CO2.

Description: The effect of elevated seawater carbon dioxide (CO2) on the activity of a natural bacterioplankton community in an Arctic fjord system was investigated by a mesocosm perturbation study in the frame of the European Project on Ocean Acidification (EPOCA). A pCO2 range of 175–1085 μatm was set up in nine mesocosms deployed in the Kongsfjorden (Svalbard). The bacterioplankton communities responded to rising chlorophyll a concentrations after a lag phase of only a few days with increasing protein production and extracellular enzyme activity and revealed a close coupling of heterotrophic bacterial activity to phytoplankton productivity in this experiment. The natural extracellular enzyme assemblages showed increased activity in response to moderate acidification. A decrease in seawater pH of 0.5 units roughly doubled rates of β-glucosidase and leucine-aminopeptidase. Activities of extracellular enzymes in the mesocosms were directly related to both seawater pH and primary production. Also primary production and bacterial protein production in the mesocosms at different pCO2 were positively correlated. Therefore, it can be suggested that the efficient heterotrophic carbon utilization in this Arctic microbial food web had the potential to counteract increased phytoplankton production that was achieved under elevated pCO2 in this study. However, our results also show that the transfer of beneficial pCO2-related effects on the cellular bacterial metabolism to the scale of community activity and organic matter degradation can be mitigated by the top-down control of bacterial abundances in natural microbial communities.

Description: The replenishment of consumed oxygen in the open ocean oxygen minimum zone (OMZ) off northwest Africa is accomplished by oxygen transport across and along density surfaces, i.e. diapycnal and isopycnal oxygen supply. Here the diapycnal oxygen supply is investigated using a large observational set of oxygen profiles and diapycnal mixing data from years 2008 to 2010. Diapycnal mixing is inferred from different sources: (i) a large-scale tracer release experiment, (ii) microstructure profiles, and (iii) shipboard acoustic current measurements plus density profiles. From these measurements, the average diapycnal diffusivity in the studied depth interval from 150 to 500m is estimated to be 1×10−5 m2 s−1, with lower and upper 95%confidence limits of 0.8×10−5 m2 s−1 and 1.4×10−5 m2 s−1. Diapycnal diffusivity in this depth range is predominantly caused by turbulence, and shows no significant vertical gradient. Diapycnal mixing is found to contribute substantially to the oxygen supply of the OMZ. Within the OMZ core, 1.5 μmol kg−1 yr−1 of oxygen is supplied via diapycnal mixing, contributing about one-third of the total demand. This oxygen which is supplied via diapycnal mixing originates from oxygen that has been laterally supplied within the upper CentralWater layer above the OMZ, and within the Antarctic Intermediate Water layer below the OMZ. Due to the existence of a separate shallow oxygen minimum at about 100m depth throughout most of the study area, there is no net vertical oxygen flux from the surface layer into the Central Water layer. Thus all oxygen supply of the OMZ is associated with remote pathways.

Description: The Arctic Ocean ecosystem is particularly vulnerable to ocean acidification (OA) related alterations due to the relatively high CO2 solubility and low carbonate saturation states of its cold surface waters. Thus far, however, there is only little known about the consequences of OA on the base of the food web. In a mesocosm CO2-enrichment experiment (overall CO2 levels ranged from ~ 180 to 1100 μatm) in Kongsfjorden off Svalbard, we studied the consequences of OA on a natural pelagic microbial community. OA distinctly affected the composition and growth of the Arctic phytoplankton community, i.e. the picoeukaryotic photoautotrophs and to a lesser extent the nanophytoplankton thrived. A shift towards the smallest phytoplankton as a result of OA will have direct consequences for the structure and functioning of the pelagic food web and thus for the biogeochemical cycles. Besides being grazed, the dominant pico- and nanophytoplankton groups were found prone to viral lysis, thereby shunting the carbon accumulation in living organisms into the dissolved pools of organic carbon and subsequently affecting the efficiency of the biological pump in these Arctic waters.

Description: The potential effect of ocean acidification (OA) on seawater halocarbons in the Arctic was investigated during a~mesocosm experiment in Spitsbergen in June–July 2010. Over a period of 5 weeks, natural phytoplankton communities in nine ~50 m3 mesocosms were studied under a range of pCO2 treatments from ~185 μatm to ~1420 μatm. In general, the response of halocarbons to pCO2 was subtle, or undetectable. A large number of significant correlations with a range of biological parameters (chlorophyll a, microbial plankton community, phytoplankton pigments) were identified, indicating a biological control on the concentrations of halocarbons within the mesocosms. The temporal dynamics of iodomethane (CH3I) alluded to active turnover of this halocarbon in the mesocosms and strong significant correlations with biological parameters suggested a biological source. However, despite a pCO2 effect on various components of the plankton community, and a strong association between CH3I and biological parameters, no effect of pCO2 was seen in CH3I. Diiodomethane (CH2I2) displayed a number of strong relationships with biological parameters. Furthermore, the concentrations, the rate of net production and the sea-to-air flux of CH2I2 showed a significant positive response to pCO2. There was no clear effect of pCO2 on bromocarbon concentrations or dynamics. However, periods of significant net loss of bromoform (CHBr3) were found to be concentration-dependent, and closely correlated with total bacteria, suggesting a degree of biological consumption of this halocarbon in Arctic waters. Although the effects of OA on halocarbon concentrations were marginal, this study provides invaluable information on the production and cycling of halocarbons in a region of the world's oceans likely to experience rapid environmental change in the coming decades.

Description: Temporal changes in the water mass distribution and biogeochemical signals in the tropical eastern South Pacific are investigated with the help of an extended optimum multi-parameter (OMP) analysis, a technique for inverse modeling of mixing and biogeochemical processes through a multidimensional least-square fit. Two ship occupations of a meridional section along 85°50' W from 14° S to 1° N are analysed during relatively warm (El Niño/El Viejo, March 1993) and cold (La Niña/La Vieja, February 2009) upper-ocean phases. The largest El Niño–Southern Oscillation (ENSO) impact was found in the water properties and water mass distribution in the upper 200 m north of 10° S. ENSO promotes the vertical motion of the oxygen minimum zone (OMZ) associated with the hypoxic equatorial subsurface water (ESSW). During a cold phase the core of the ESSW is found at shallower layers, replacing shallow (top 200 m) subtropical surface water (STW). The heave of isopycnals due to ENSO partially explains the intrusion of oxygen-rich and nutrient-poor antarctic intermediate water (AAIW) into the depth range of 150–500 m. The other cause of the AAIW increase at shallower depths is that this water mass flowed along shallower isopycnals in 2009. The shift in the vertical location of AAIW reaching the OMZ induces changes in the amount of oxygen advected and respired inside the OMZ: the larger the oxygen supply, the greater the respiration and the lower the nitrate loss through denitrification. Variations in the intensity of the zonal currents in the equatorial current system, which ventilates the OMZ from the west, are used to explain the patchy latitudinal changes of seawater properties observed along the repeated section. Significant changes reach down to 800 m, suggesting that decadal variability (Pacific decadal oscillation) is also a potential driver in the observed variability.

Description: The accumulation of gas hydrates in marine sediments is essentially controlled by the accumulation of particulate organic carbon (POC) which is microbially converted into methane, the thickness of the gas hydrate stability zone (GHSZ) where methane can be trapped, the sedimentation rate (SR) that controls the time that POC and the generated methane stays within the GHSZ, and the delivery of methane from deep-seated sediments by ascending pore fluids and gas into the GHSZ. Recently, Wallmann et al. (2012) presented transfer functions to predict the gas hydrate inventory in diffusion-controlled geological systems based on SR, POC and GHSZ thickness for two different scenarios: normal and full compacting sediments. We apply these functions to global data sets of bathymetry, heat flow, seafloor temperature, POC input and SR, estimating a global mass of carbon stored in marine methane hydrates from 3 to 455 Gt of carbon (GtC) depending on the sedimentation and compaction conditions. The global sediment volume of the GHSZ in continental margins is estimated to be 60–67 × 1015 m3, with a total of 7 × 1015 m3 of pore volume (available for GH accumulation). However, seepage of methane-rich fluids is known to have a pronounced effect on gas hydrate accumulation. Therefore, we carried out a set of systematic model runs with the transport-reaction code in order to derive an extended transfer function explicitly considering upward fluid advection. Using averaged fluid velocities for active margins, which were derived from mass balance considerations, this extended transfer function predicts the enhanced gas hydrate accumulation along the continental margins worldwide. Different scenarios were investigated resulting in a global mass of sub-seafloor gas hydrates of ~ 550 GtC. Overall, our systematic approach allows to clearly and quantitatively distinguish between the effect of biogenic methane generation from POC and fluid advection on the accumulation of gas hydrate, and hence, provides a simple prognostic tool for the estimation of large-scale and global gas hydrate inventories in marine sediments.

Description: This paper presents the application of the Linear Quadratic Optimal Control (LQOC) method to a parameter optimization problem for a one-dimensional marine ecosystem model of NPZD (N for dissolved inorganic nitrogen, P for phytoplankton, Z for zooplankton and D for detritus) type. This ecosystem model, developed by Oschlies and Garcon, simulates the distribution of nitrogen, phytoplankton, zooplankton and detritus in a water column and is driven by ocean circulation data. The LQOC method is used to introduce annually periodic model parameters in a linearized version of the model. We show that the obtained version of the model gives a significant reduction of the model-data misfit, compared to the one obtained for the original model with optimized constant parameters. The found inner-annual variability of the optimized parameters provides hints for improvement of the original model. We use the obtained optimal periodic parameters also in validation and prediction experiments with the original non-linear version of the model. In both cases, the results are significantly better than those obtained with optimized constant parameters.

Description: Mesocosms as large experimental vessels principally provide the opportunity of performing elemental budget calculations e.g. to derive net biological turnover rates. However, the system is in most cases not closed at the water surface and gases can exchange with the atmosphere. Previous attempts to budget carbon pools in mesocosms relied on educated guesses concerning the exchange of CO2 with the atmosphere. Nevertheless, net primary production rates derived from these budget calculations were, despite large uncertainties in air/sea gas exchange, often more reasonable than cumulative extrapolations of bioassays. While bioassays have limitations representing the full spectrum of trophic levels and abiotic conditions inside the mesocosms, calculating dissolved inorganic carbon uptake inside the mesocosms has the potential to deliver net community production rates representative of the enclosed system. Here, we present a simple method for precise determination of air/sea gas exchange velocities in mesocosms using N2O as a deliberate tracer. Beside the application for carbon budgeting, exchange velocities can be used to calculate exchange rates of any gas of known concentration, e.g. to calculate aquatic production rates of climate relevant trace gases. Using an arctic (Kiel Off Shore Mesocosms for future Ocean Simulation) mesocosm experiment as an exemplary dataset, it is shown that application of the presented method largely improves accuracy of carbon budget estimates. Methodology of manipulation, measurement, data processing and conversion to CO2 fluxes are explained. A theoretical discussion of prerequisites for precise gas exchange measurements provides a guideline for the applicability of the method under various experimental conditions.

Description: The lack of long and reliable time series of solar spectral irradiance (SSI) measurements makes an accurate quantification of solar contributions to recent climate change difficult. Whereas earlier SSI observations and models provided a qualitatively consistent picture of the SSI variability, recent measurements by the SORCE (SOlar Radiation and Climate Experiment) satellite suggest a significantly stronger variability in the ultraviolet (UV) spectral range and changes in the visible and near-infrared (NIR) bands in anti-phase with the solar cycle. A number of recent chemistry-climate model (CCM) simulations have shown that this might have significant implications on the Earth's atmosphere. Motivated by these results, we summarize here our current knowledge of SSI variability and its impact on Earth's climate. We present a detailed overview of existing SSI measurements and provide thorough comparison of models available to date. SSI changes influence the Earth's atmosphere, both directly, through changes in shortwave (SW) heating and therefore, temperature and ozone distributions in the stratosphere, and indirectly, through dynamical feedbacks. We investigate these direct and indirect effects using several state-of-the art CCM simulations forced with measured and modelled SSI changes. A unique asset of this study is the use of a common comprehensive approach for an issue that is usually addressed separately by different communities. We show that the SORCE measurements are difficult to reconcile with earlier observations and with SSI models. Of the five SSI models discussed here, specifically NRLSSI (Naval Research Laboratory Solar Spectral Irradiance), SATIRE-S (Spectral And Total Irradiance REconstructions for the Satellite era), COSI (COde for Solar Irradiance), SRPM (Solar Radiation Physical Modelling), and OAR (Osservatorio Astronomico di Roma), only one shows a behaviour of the UV and visible irradiance qualitatively resembling that of the recent SORCE measurements. However, the integral of the SSI computed with this model over the entire spectral range does not reproduce the measured cyclical changes of the total solar irradiance, which is an essential requisite for realistic evaluations of solar effects on the Earth's climate in CCMs. We show that within the range provided by the recent SSI observations and semi-empirical models discussed here, the NRLSSI model and SORCE observations represent the lower and upper limits in the magnitude of the SSI solar cycle variation. The results of the CCM simulations, forced with the SSI solar cycle variations estimated from the NRLSSI model and from SORCE measurements, show that the direct solar response in the stratosphere is larger for the SORCE than for the NRLSSI data. Correspondingly, larger UV forcing also leads to a larger surface response. Finally, we discuss the reliability of the available data and we propose additional coordinated work, first to build composite SSI data sets out of scattered observations and to refine current SSI models, and second, to run coordinated CCM experiments.

Description: Responses to ocean acidification in plankton communities were studied during a CO2-enrichment experiment in the Arctic Ocean, accomplished from June to July 2010 in Kongsfjorden, Svalbard (78°56′ 2′′ N, 11°53′ 6′′ E). Enclosed in 9 mesocosms (volume: 43.9–47.6 m3), plankton was exposed to CO2 concentrations, ranging from glacial to projected mid-next-century levels. Fertilization with inorganic nutrients at day 13 of the experiment supported the accumulation of phytoplankton biomass, as indicated by two periods of high chl a concentration. This study tested for CO2 sensitivities in primary production (PP) of particulate organic carbon (PPPOC) and of dissolved organic carbon (PPDOC). Therefore, 14C-bottle incubations (24 h) of mesocosm samples were performed at 1 m depth receiving about 60% of incoming radiation. PP for all mesocosms averaged 8.06 ± 3.64 μmol C L−1 d−1 and was slightly higher than in the outside fjord system. Comparison between mesocosms revealed significantly higher PPPOC at elevated compared to low pCO2 after nutrient addition. PPDOC was significantly higher in CO2-enriched mesocosms before as well as after nutrient addition, suggesting that CO2 had a direct influence on DOC production. DOC concentrations inside the mesocosms increased before nutrient addition and more in high CO2 mesocosms. After addition of nutrients, however, further DOC accumulation was negligible and not significantly different between treatments, indicating rapid utilization of freshly produced DOC. Bacterial biomass production (BP) was coupled to PP in all treatments, indicating that 3.5 ± 1.9% of PP or 21.6 ± 12.5% of PPDOC provided on average sufficient carbon for synthesis of bacterial biomass. During the later course of the bloom, the response of 14C-based PP rates to CO2 enrichment differed from net community production (NCP) rates that were also determined during this mesocosm campaign. We conclude that the enhanced release of labile DOC during autotrophic production at high CO2 exceedingly stimulated activities of heterotrophic microorganisms. As a consequence, increased PP induced less NCP, as suggested earlier for carbon-limited microbial systems in the Arctic.

Description: The increasing CO2 concentration in the atmosphere caused by burning fossil fuels leads to increasing pCO2 and decreasing pH in the world oceans. These changes may have severe consequences for marine biota, especially in cold-water ecosystems due to higher solubility of CO2. However, studies on the response of mesozooplankton communities to elevated pCO2 are yet lacking. In order to test whether abundance and taxonomic composition change with pCO2, we have sampled nine mesocosms, which were deployed in Kongsfjorden, an Arctic fjord at Svalbard, and were adjusted to eight CO2 concentrations, initially ranging from 185 μatm to 1420 μatm. Samples were taken weekly over a six-week period with an Apstein net (55 μm mesh size) in all mesocosms and the surrounding fjord. In addition, sediment trap samples, taken every second day in the mesocosms, were analyzed to account for losses due to vertical migration and mortality. The taxonomic analysis revealed that meroplanktonic larvae (cirripeds, polychaetes, bivalves, gastropod, and decapods) dominated in the mesocosms while copepods (Calanus spp., Oithona similis, Acartia longiremis and Microsetella norvegica) were found in lower abundances. In the fjord copepods prevailed for most of our study. With time, abundance and taxonomic composition developed similarly in all mesocosms; the pCO2 had no significant effect on the overall community structure. However, single taxa responded to elevated CO2 concentrations. The ratio of cirripedia nauplii to cypris larvae, the next developmental stage, in the sediment traps averaged over the entire experiment increased with pCO2 and this suggests that increased pCO2 may have delayed their development. Also, the number of bivalves, averaged over the experimental period, decreased significantly with increasing pCO2. The nature of the CO2 effect, either direct or indirect, remains open and needs to be addressed in future.

Description: The filamentous and diazotrophic cyanobacterium Nodularia spumigena plays a major role in the productivity of the Baltic Sea as it forms extensive blooms regularly. Under phosphorus limiting conditions Nodularia spumigena has a high enzyme affinity for dissolved organic phosphorus (DOP) by production and release of alkaline phosphatase. Additionally, it is able to degrade proteinaceous compounds by expressing the extracellular enzyme leucine aminopeptidase. As atmospheric CO2 concentrations are increasing, we expect marine phytoplankton to experience changes in several environmental parameters including pH, temperature, and nutrient availability. The aim of this study was to investigate the combined effect of CO2-induced changes in seawater carbonate chemistry and of phosphate deficiency on the exudation of organic matter, and its subsequent recycling by extracellular enzymes in a Nodularia spumigena culture. Batch cultures of Nodularia spumigena were grown for 15 days aerated with three different pCO2 levels corresponding to values from glacial periods to future values projected for the year 2100. Extracellular enzyme activities as well as changes in organic and inorganic compound concentrations were monitored. CO2 treatment–related effects were identified for cyanobacterial growth, which in turn was influencing exudation and recycling of organic matter by extracellular enzymes. Biomass production was increased by 56.5% and 90.7% in the medium and high pCO2 treatment, respectively, compared to the low pCO2 treatment and simultaneously increasing exudation. During the growth phase significantly more mucinous substances accumulated in the high pCO2 treatment reaching 363 μg Gum Xanthan eq l−1 compared to 269 μg Gum Xanthan eq l−1 in the low pCO2 treatment. However, cell-specific rates did not change. After phosphate depletion, the acquisition of P from DOP by alkaline phosphatase was significantly enhanced. Alkaline phosphatase activities were increased by factor 1.64 and 2.25, respectively, in the medium and high compared to the low pCO2 treatment. In conclusion, our results suggest that Nodularia spumigena can grow faster under elevated pCO2 by enhancing the recycling of organic matter to acquire nutrients.

Description: Methane and carbon dioxide were measured with an autonomous and continuous running system on a ferry line crossing the Baltic Sea on a 2–3 day interval from the Mecklenburg Bight to the Gulf of Finland in 2010. Surface methane saturations show great seasonal differences in shallow regions like the Mecklenburg Bight (103–507 %) compared to deeper regions like the Gotland Basin (96–161 %). The influence of controlling parameters like temperature, wind, mixing depth and processes like upwelling, mixing of the water column and sedimentary methane emissions on methane oversaturation and emission to the atmosphere are investigated. Upwelling was found to influence methane surface concentrations in the area of Gotland significantly during the summer period. In February 2010, an event of elevated methane concentrations in the surface water and water column of the Arkona Basin was observed, which could be linked to a wind-derived water level change as a potential triggering mechanism. The Baltic Sea is a source of methane to the atmosphere throughout the year, with highest fluxes occurring during the winter season. Stratification was found to promote the formation of a methane reservoir in deeper regions like Gulf of Finland or Bornholm Basin, which leads to long lasting elevated methane concentrations and enhanced methane fluxes, when mixed to the surface during mixed layer deepening in autumn and winter. Methane concentrations and fluxes from shallow regions like the Mecklenburg Bight are predominantly controlled by sedimentary production and consumption of methane, wind events and the change in temperature-dependent solubility of methane in the surface water. Methane fluxes vary significantly in shallow regions (e.g. Mecklenburg Bight) and regions with a temporal stratification (e.g. Bornholm Basin, Gulf of Finland). On the contrary, areas with a permanent stratification like the Gotland Basin show only small seasonal fluctuations in methane fluxes.

Description: A latitudinal cross-section and vertical profiles of iodine monoxide (IO) are reported from the marine boundary layer of the Western Pacific. The measurements were taken using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) during the TransBrom cruise of the German research vessel Sonne, which led from Tomakomai, Japan (42° N, 141° E) through the Western Pacific to Townsville, Australia (19° S, 146° E) in October 2009. In the marine boundary layer within the tropics (between 20° N and 5° S), IO mixing ratios ranged between 1 and 2.2 ppt, whereas in the subtropics and at mid-latitudes typical IO mixing ratios were around 1 ppt in the daytime. The profile retrieval reveals that the bulk of the IO was located in the lower part of the marine boundary layer. Photochemical simulations indicate that the organic iodine precursors observed during the cruise (CH3I, CH2I2, CH2ClI, CH2BrI) are not sufficient to explain the measured IO mixing ratios. Reasonable agreement between measured and modelled IO can only be achieved, if an additional sea-air flux of inorganic iodine (e.g. I2) is assumed in the model. Our observations add further evidence to previous studies that reactive iodine is an important oxidant in the marine boundary layer.

Description: Climatologies of atmospheric observations are often produced by binning measurements according to latitude, and calculating zonal means. The uncertainty in these climatological means is characterized by the standard error of the mean (SEM). However, the usual estimator of the SEM, i.e. the sample standard deviation divided by the square root of the sample size, holds only for uncorrelated randomly sampled measurements. Measurements of the atmospheric state along a satellite orbit cannot always be considered as independent because (a) the time-space interval between two nearest observations is often smaller than the typical scale of variations in the atmospheric state, and (b) the regular time-space sampling pattern of a satellite instrument strongly deviates from random sampling. We have developed an experiment where global chemical fields from a chemistry climate model are sampled according to real sampling patterns of satellite-borne instruments. As case studies, sampling patterns of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) and Atmospheric Chemistry Experiment Fourier-Transform Spectrometer (ACE-FTS) satellite instruments are used to iteratively subsample the model O3 fields and produce empirical estimates of the standard error of monthly mean zonal mean model O3 in 5° latitude bins. We find that generally the classic SEM estimator is a conservative estimate of the SEM, i.e. the empirical SEM is often less than the classic estimate. Exceptions occur in instances where the zonal sampling distribution shows non-uniformity with a similar zonal structure as variations in the sampled field, leading to maximum sensitivity to arbitrary phase shifts between the sample distribution and sampled field. The occurrence of such instances is thus very sensitive to slight changes in the sampling distribution, and to the variations in the measured field. This study highlights the need for caution in the interpretation of the oft-used classically computed SEM, and outlines a relatively simple methodology that can be used to assess one component of the uncertainty in monthly mean zonal mean climatologies produced from measurements from satellite-borne instruments

Description: The discovery that foraminifera are able to use nitrate instead of oxygen as energy source for their metabolism has challenged our understanding of nitrogen cycling in the ocean. It was evident before that only prokaryotes and fungi are able to denitrify. Rate 5 estimates of foraminiferal denitrification were very sparse on a regional scale. Here, we present estimates of benthic foraminiferal denitrification rates from six stations at intermediate water depths in and below the Peruvian oxygen minimum zone (OMZ). Foraminiferal denitrification rates were calculated from abundance and assemblage composition of the total living fauna in both, surface and subsurface sediments, 10 as well as from individual species specific denitrification rates. A comparison with total benthic denitrification rates as inferred by biogeochemical models revealed that benthic foraminifera account for the total denitrification on the shelf between 80 and 250m water depth. They are still important denitrifiers in the centre of the OMZ around 320m (29–56% of the benthic denitrification) but play only a minor role at the lower OMZ 15 boundary and below the OMZ between 465 and 700m (3–7% of total benthic denitrification). Furthermore, foraminiferal denitrification was compared to the total benthic nitrate loss measured during benthic chamber experiments. Foraminiferal denitrification contributes 1 to 50% to the total nitrate loss across a depth transect from 80 to 700 m, respectively. Flux rate estimates ranged from 0.01 to 1.3 mmolm−2 d−1. Fur20 thermore we show that the amount of nitrate stored in living benthic foraminifera (3 to 705 μmolL−1) can be higher by three orders of magnitude as compared to the ambient pore waters in near surface sediments sustaining an important nitrate reservoir in Peruvian OMZ sediments. The substantial contribution of foraminiferal nitrate respiration to total benthic nitrate loss at the Peruvian margin, which is one of the main nitrate sink 25 regions in the world oceans, underpins the importance of previously underestimated role of benthic foraminifera in global biochemical cycles.

Description: Pacific Ocean sea surface temperatures (SST) influence rainfall variability on multidecadal and interdecadal timescales in concert with the Pacific Decadal Oscillation (PDO) and Interdecadal Pacific Oscillation (IPO). Rainfall variations in locations such as Australia and North America are therefore linked to phase changes in the PDO. Furthermore, studies have suggested teleconnections exist between the western Indian Ocean and Pacific Decadal Variability (PDV), similar to those observed on interannual timescales related to the El Niño Southern Oscillation (ENSO). However, as instrumental records of rainfall are too short and sparse to confidently assess multidecadal climatic teleconnections, here we present four coral climate archives from Madagascar spanning up to the past 300 yr (1708–2008) to assess such decadal variability. Using spectral luminescence scanning to reconstruct past changes in river runoff, we identify significant multidecadal and interdecadal frequencies in the coral records, which before 1900 are coherent with Asian-based PDO reconstructions. This multidecadal relationship with the Asian-based PDO reconstructions points to an unidentified teleconnection mechanism that affects Madagascar rainfall/runoff, most likely triggered by multidecadal changes in North Pacific SST, influencing the Asian Monsoon circulation. In the 20th century we decouple human deforestation effects from rainfall-induced soil erosion by pairing luminescence with coral geochemistry. Positive PDO phases are associated with increased Indian Ocean temperatures and runoff/rainfall in eastern Madagascar, while precipitation in southern Africa and eastern Australia declines. Consequently, the negative PDO phase that started in 1998 may contribute to reduced rainfall over eastern Madagascar and increased precipitation in southern Africa and eastern Australia. We conclude that multidecadal rainfall variability in Madagascar and the western Indian Ocean needs to be taken into account when considering water resource management under a future warming climate.

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: El Niño–Southern Oscillation (ENSO) in the Pacific and the analogous Atlantic Niño mode are generated by processes involving coupled ocean–atmosphere interactions known as the Bjerknes feedback. It has been argued that the Atlantic Niño mode is more strongly damped than ENSO, which is presumed to be closer to neutrally stable. In this study the stability of ENSO and the Atlantic Niño mode is compared via an analysis of the Bjerknes stability index. This index is based on recharge oscillator theory and can be interpreted as the growth rate for coupled modes of ocean–atmosphere variability. Using observational data, an ocean reanalysis product, and output from an ocean general circulation model, the individual terms of the Bjerknes index are calculated for the first time for the Atlantic and then compared to results for the Pacific. Positive thermocline feedbacks in response to wind stress forcing favor anomaly growth in both basins, but they are twice as large in the Pacific compared to the Atlantic. Thermocline feedback is related to the fetch of the zonal winds, which is much greater in the equatorial Pacific than in the equatorial Atlantic due to larger basin size. Negative feedbacks are dominated by thermal damping of sea surface temperature anomalies in both basins. Overall, it is found that both ENSO and the Atlantic Niño mode are damped oscillators, but the Atlantic is more strongly damped than the Pacific primarily because of the weaker thermocline feedback.

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")