Gridded bathymetry from multibeam echosounder EM122 data of the cruise MSM34/2 (2013)

Bathymetry based on data recorded during MSM34-2 between 27.12.2013 and 18.01.2014 in the Black Sea. The main objective of this cruise was the mapping and imaging of the gas hydrate distribution and gas accumulations as well as possible gas migration pathways. Objectives of Cruise: Gas hydrates have been the focus of scientific and economic interest for the past 15-20 years, mainly because the amount of carbon stored in gas hydrates is much greater than in other carbon reservoirs. Several countries including Japan, Korea and India have launched vast reasearch programmes dedicated to the exploration for gas hydrate resources and ultimately the exploitation of the gas hydrates for methane. The German SUGAR project that is financed the the Ministry of Education and Research (BmBF) and the Ministry of Economics (BmWi) aims at developing technology to exploit gas hydrate resources by injecting and storing CO2 instead of methane in the hydrates. This approach includes techniques to locate and quantify hydrate reservoirs, drill into the reservoir, extract methane from the hydrates by replacing it with CO2, and monitor the thus formed CO2-hydrate reservoir. Numerical modeling has shown that any exploitation of the gas hydrates can only be succesful, if sufficient hydrate resources are present within permeable reservoirs such as sandy or gravelly deposits. The ultimate goal of the SUGAR project being a field test of the technology developed within the project, knowledge of a suitable test site becomes crucial. Within European waters only the Norwegian margin and the Danube deep-sea fan show clear geophysical evidence for large gas hydrate accumulations, but only the Danube deep-sea fan most likely contains gas hydrates within sandy deposits. The main objective of cruise MSM34 therefore is locating and characterising suitable gas hydrate deposits on the Danube deep-sea fan.

Contrasting effects of ocean acidification on reproduction in reef fishes

Differences in the sensitivity of marine species to ocean acidification will influence the structure of marine communities in the future. Reproduction is critical for individual and population success, yet is energetically expensive and could be adversely affected by rising CO2 levels in the ocean. We investigated the effects of projected future CO2 levels on reproductive output of two species of coral reef damselfish, Amphiprion percula and Acanthochromis polyacanthus. Adult breeding pairs were maintained at current-day control (446 µatm), moderate (652 µatm) or high CO2 (912 µatm) for a 9-month period that included the summer breeding season. The elevated CO2 treatments were consistent with CO2 levels projected by 2100 under moderate (RCP6) and high (RCP8) emission scenarios. Reproductive output increased in A. percula, with 45-75 % more egg clutches produced and a 47-56 % increase in the number of eggs per clutch in the two elevated CO2 treatments. In contrast, reproductive output decreased at high CO2 in Ac. polyacanthus, with approximately one-third as many clutches produced compared with controls. Egg survival was not affected by CO2 for A. percula, but was greater in elevated CO2 for Ac. polyacanthus. Hatching success was also greater for Ac. polyacanthus at elevated CO2, but there was no effect of CO2 treatments on offspring size. Despite the variation in reproductive output, body condition of adults did not differ between control and CO2 treatments in either species. Our results demonstrate different effects of high CO2 on fish reproduction, even among species within the same family. A greater understanding of the variation in effects of ocean acidification on reproductive performance is required to predict the consequences for future populations of marine organisms.

Mineral nitrogen from KCl extractions of soil from the Jena Experiment (Main Experiment up to 30cm depth, year 2003)

As an estimate of plant-available N, this data set contains measurements of inorganic nitrogen (NO3-N and NH4-N, the sum of which is termed mineral N or Nmin) determined by extraction with 1 M KCl solution of soil samples from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Five soil cores (diameter 0.01 m) were taken at a depth of 0 to 0.15 m and 0.15 to 0.3 m of the mineral soil from each of the experimental plots in March, June, and October 2003. Samples of the soil cores per plot were pooled during each sampling campaign. NO3-N and NH4-N concentrations were determined by extraction of soil samples with 1 M KCl solution and were measured in the soil extract with a Continuous Flow Analyzer (CFA, Skalar, Breda, Netherlands).

Effects of increasing seawater carbon dioxide concentrations on chain formation of the diatom Asterionellopsis glacialis

Diatoms can occur as single cells or as chain-forming aggregates. These two strategies affect buoyancy, predator evasion, light absorption and nutrient uptake. Adjacent cells in chains establish connections through various processes that determine strength and flexibility of the bonds, and at distinct cellular locations defining colony structure. Chain length has been found to vary with temperature and nutrient availability as well as being positively correlated with growth rate. However, the potential effect of enhanced carbon dioxide (CO2) concentrations and consequent changes in seawater carbonate chemistry on chain formation is virtually unknown. Here we report on experiments with semi-continuous cultures of the freshly isolated diatom Asterionellopsis glacialis grown under increasing CO2 levels ranging from 320 to 3400 µatm. We show that the number of cells comprising a chain, and therefore chain length, increases with rising CO2 concentrations. We also demonstrate that while cell division rate changes with CO2 concentrations, carbon, nitrogen and phosphorus cellular quotas vary proportionally, evident by unchanged organic matter ratios. Finally, beyond the optimum CO2 concentration for growth, carbon allocation changes from cellular storage to increased exudation of dissolved organic carbon. The observed structural adjustment in colony size could enable growth at high CO2 levels, since longer, spiral-shaped chains are likely to create microclimates with higher pH during the light period. Moreover increased chain length of Asterionellopsis glacialis may influence buoyancy and, consequently, affect competitive fitness as well as sinking rates. This would potentially impact the delicate balance between the microbial loop and export of organic matter, with consequences for atmospheric carbon dioxide.

(Table 1) U and Th isotopic composition and 230Th ages of samples from the A1 and C1 corals of Legare Anchorage

The 14C reservoir age of the surface ocean was determined for two Holocene periods (4908-4955 and 3008-3066 calendar (cal) B.P.) using U/Th-dated corals from Biscayne National Park, Florida, United States. We found that the average reservoir ages for these two time periods (294 ± 33 and 291 ± 27 years, respectively) were lower than the average value between A.D. 1600 and 1900 (390 ± 60 years) from corals. It appears that the surface ocean was closer to isotopic equilibrium with CO2 in the atmosphere during these two time periods than it was during recent times. Seasonal d18O measurements from the younger coral are similar to modern values, suggesting that mixing with open ocean waters was indeed occurring during this coral's lifetime. Likely explanations for the lower reservoir age include increased stratification of the surface ocean or increased D14C values of subsurface waters that mix into the surface. Our results imply that a more correct reservoir age correction for radiocarbon measurements of marine samples in this location from the time periods ~3040 and ~4930 cal years B.P. is ~292 ± 30 years, less than the canonical value of 404 ± 20 years.

(Table 1) Mean grain sizes and standard deviations of gas hydrate samples

Methane hydrates are present in marine seep systems and occur within the gas hydrate stability zone. Very little is known about their crystallite sizes and size distributions because they are notoriously difficult to measure. Crystal size distributions are usually considered as one of the key petrophysical parameters because they influence mechanical properties and possible compositional changes, which may occur with changing environmental conditions. Variations in grain size are relevant for gas substitution in natural hydrates by replacing CH4 with CO2 for the purpose of carbon dioxide sequestration. Here we show that crystallite sizes of gas hydrates from some locations in the Indian Ocean, Gulf of Mexico and Black Sea are in the range of 200-400 µm; larger values were obtained for deeper-buried samples from ODP Leg 204. The crystallite sizes show generally a log-normal distribution and appear to vary sometimes rapidly with location.

Mesocosm experiment on warming and acidification effects on phytoplankton composition and cell size

While the isolated responses of marine phytoplankton to climate warming and to ocean acidification have been studies intensively, studies on the combined effect of both aspects of Global Change are still scarce. Therefore, we performed a mesocosm experiment with a factorial combination of temperature (9 and 15°C) and pCO2 (560 ppm and 1400 ppm) with a natural autumn plankton community from the western Baltic Sea. Temporal trajectories of total biomass and of the biomass of the most important higher taxa followed similar patterns in all treatments. When averaging over the entire time course, phytoplankton biomass decreased with warming and increased with CO2 under warm conditions. The contribution of the two dominant higher phytoplankton taxa (diatoms and cryptophytes) and of the 4 most important species (3 diatoms, 1 cryptophyte) did not respond to the experimental treatments. Taxonomic composition of phytoplankton showed only responses at the level of subdominant and rare species. Phytoplankton cell sizes increased with CO2 addition and decreased with warming. Both effects were stronger for larger species. Warming effects were stronger than CO2 effects and tended to counteract each other. Phytoplankton communities without calcifying species and exposed to short-term variation of COO2 seem to be rather resistant to ocean acidification.

(Table 1) Oxygen isotopic composition of interstitial waters from ODP Hole 161-976

Interstitial waters recovered from Ocean Drilling Program, Leg 161, site 976 in the western Mediterranean Sea are used in conjunction with a numerical model to constrain the delta18O of seawater in the basin since the Last Glacial Maximum, including Sapropel Event 1. To resolve the oxygen isotopic composition of the deep Mediterranean, we use a model that couples fluid diffusion with advective transport, thus producing a profile of seawater delta18O variability that is unaffected by glacial-interglacial variations in marine temperature. Comparing our reconstructed seawater delta18O to recent determinations of 1.0 per mil for the mean ocean change in glacial-interglacial delta18O due to the expansion of global ice volume, we calculate an additional 0.2 per mil increase in Mediterranean delta18O caused by local evaporative enrichment. This estimate of delta18O change, due to salinity variability, is smaller than previous studies have proposed and demonstrates that Mediterranean records of foraminiferal calcite delta18O from the last glacial period include a strong temperature component. Paleotemperatures determined in combination with a stacked record of foraminiferal calcite depict almost 9°C of regional cooling for the Last Glacial Maximum. Model results suggest a decrease of ~1.1 per mil in seawater delta18O relative to the modern value caused by increased freshwater input and reduced salinity accompanying the formation of the most recent sapropel. The results additionally indicate the existence of isotopically light water circulating down to bottom water depths, at least in the western Mediterranean, supporting the existence of an 'anti-estuarine' thermohaline circulation pattern during Sapropel Event 1.

Geochemical analyses and Delta47 values in shallow water corals

Geochemical variations in shallow water corals provide a valuable archive of paleoclimatic information. However, biological effects can complicate the interpretation of these proxies, forcing their application to rely on empirical calibrations. Carbonate clumped isotope thermometry (Delta47) is a novel paleotemperature proxy based on the temperature dependent "clumping" of 13C-18O bonds. Similar ?47-temperature relationships in inorganically precipitated calcite and a suite of biogenic carbonates provide evidence that carbonate clumped isotope variability may record absolute temperature without a biological influence. However, large departures from expected values in the winter growth of a hermatypic coral provided early evidence for possible Delta47 vital effects. Here, we present the first systematic survey of Delta47 in shallow water corals. Sub-annual Red Sea Delta47 in two Porites corals shows a temperature dependence similar to inorganic precipitation experiments, but with a systematic offset toward higher Delta47 values that consistently underestimate temperature by ~8 °C. Additional analyses of Porites, Siderastrea, Astrangia and Caryophyllia corals argue against a number of potential mechanisms as the leading cause for this apparent Delta47 vital effect including: salinity, organic matter contamination, alteration during sampling, the presence or absence of symbionts, and interlaboratory differences in analytical protocols. However, intra- and inter-coral comparisons suggest that the deviation from expected Delta47 increases with calcification rate. Theoretical calculations suggest this apparent link with calcification rate is inconsistent with pH-dependent changes in dissolved inorganic carbon speciation and with kinetic effects associated with CO2 diffusion into the calcifying space. However, the link with calcification rate may be related to fractionation during the hydration/hydroxylation of CO2 within the calcifying space. Although the vital effects we describe will complicate the interpretation of Delta47 as a paleothermometer in shallow water corals, it may still be a valuable paleoclimate proxy, particularly when applied as part of a multi-proxy approach.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

Determination of Uranium, Thorium, and Ionium in sediment cores of the Caribbean and Ionian Sea

A rapid procedure for Io (Th230) dating of sediments with accumulation rates in the range of several cm/1000 years is described. Studying of large sample populations with very small Io-excess activity is possible as the counting time (around 1500 min/sample) are 2 to 5 times shorter than with the standard Io-excess method. Improved sensitivity of the Io-excess measurement is achieved by: 1) extraction ( ~90 %) of the authigenic Io-excess with EDTA, with minor leaching ( ~30 %) of the allogenic Th232 and Io-supported, 2) processing samples as large as 10 g or more. The procedure was applied to sediments from the Caribbean (V 12-122) and from the Ionian Sea (M22_48 and M17_17). In the case of the standard core V 12-122 our results are in good agreement with previous time-consuming Io determinations. The resulting average accumulation rates of 2.0 ± 0.3 cm/1000 years for the Ionian Sea cores are close to the average derived from magnetic reversal studies of a nearby core.

Seawater carbonate chemistry and severe tissue damage in Atlantic cod larvae under increasing ocean acidification, 2012

Ocean acidification, caused by increasing atmospheric concentrations of CO2, is one of the most critical anthropogenicthreats to marine life. Changes in seawater carbonate chemistry have the potential to disturb calcification, acid-base regulation, blood circulation and respiration, as well as the nervous system of marine organisms, leading to long-term effects such as reduced growth rates and reproduction. In teleost fishes, early life-history stages are particularly vulnerable as they lack specialized internal pH regulatory mechanisms. So far, impacts of relevant CO2concentrations on larval fish have been found in behaviour and otolith size, mainly in tropical, non-commercial species. Here we show detrimental effects of ocean acidification on the development of a mass-spawning fish species of high commercial importance. We reared Atlantic cod larvae at three levels of CO2, (1) present day, (2) end of next century and (3) an extreme, coastal upwelling scenario, in a long-term ( 2.5 1/2 months) mesocosm experiment. Exposure to CO2 resulted in severe to lethal tissue damage in many internal organs, with the degree of damage increasing with CO2 concentration. As larval survival is the bottleneck to recruitment, ocean acidification has the potential to act as an additional source of natural mortality, affecting populations of already exploited fish stocks.