The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Historical sea ice of the Baltic Sea (1960/61-78/79)

The Baltic Sea is a seasonally ice-covered, marginal sea in central northern Europe. It is an essential waterway connecting highly industrialised countries. Because ship traffic is intermittently hindered by sea ice, the local weather services have been monitoring sea ice conditions for decades. In the present study we revisit a historical monitoring data set, covering the winters 1960/1961 to 1978/1979. This data set, dubbed Data Bank for Baltic Sea Ice and Sea Surface Temperatures (BASIS) ice, is based on hand-drawn maps that were collected and then digitised in 1981 in a joint project of the Finnish Institute of Marine Research (today the Finnish Meteorological Institute (FMI)) and the Swedish Meteorological and Hydrological Institute (SMHI). BASIS ice was designed for storage on punch cards and all ice information is encoded by five digits. This makes the data hard to access. Here we present a post-processed product based on the original five-digit code. Specifically, we convert to standard ice quantities (including information on ice types), which we distribute in the current and free Network Common Data Format (NetCDF). Our post-processed data set will help to assess numerical ice models and provide easy-to-access unique historical reference material for sea ice in the Baltic Sea. In addition we provide statistics showcasing the data quality. The website http://www.baltic-ocean.org hosts the post-processed data and the conversion code.

Carbonate system during the May 2013 MedSeA cruise

Most global ocean models are based on the assumption of a "steady state" ocean. Here, we investigate the validation of this hypothesis for the anthropized Mediterranean Sea. In order to do so, we calculated the mixing coefficients of the water masses detected in this sea via an optimum multiparameter analysis referred to as the MIX approach, using data from the BOUM (2008) and MedSeA (2013) cruises. The comparison of the mixing coefficients of each water mass, between 2008 and 2013, indicates that some of their proportions have significantly changed. Surface water mass proportions did not change significantly (Delta0.05-0.1), while intermediate and deep water mass mixing coefficients of both Eastern and Western basins were significantly modified (~Delata 0.35). This study clearly shows that the Mediterranean seawater is not in a "steady state".

The effect of a reduction of nitrogen and phosphorus to eutrophic and mesotrophic conditions towards silver nanoparticle (AgNP) on freshwater green algae species

We investigated the sensitivity of algae towards silver nanoparticles with OECD test medium and lower nutrient concentrations under standard test conditions to improve comparability and to exclude any other confounding factor aside nutrient levels. Two unicellular freshwater microalgae Desmodesmus subspicatus and Raphidocelis subcapitata were chosen due to their status as standard test organisms for the algae growth inhibition test and the response to changes in nutrient supply was compared. The original medium was used as the reference (standard). For the other four media, the amount of either nitrogen or phosphorus in the medium was lowered from half (50%) to one-fourth (25 %) of that of the OECD guideline, resulting in the following media: 50% N, 25% N, 50% P and 25% P medium. As test substance, the OECD reference material NM-300K was used. For this reason, the characterization of AgNP was done using DLS and Absorption spectra (UV/vis). Actual silver concentrations and ionic silver concentrations were measured at the highest test concentration used (100 µg Ag L-1) in R. subcapitata treatments only to reduce the number of samples. All tests were run according to the OECD guideline 201 with sterilized 50 mL cell culture flask. Each medium was tested using the test conditions for culturing with 3 replicates. Test concentrations for both algae species were 0, 25, 50 and 100 µg Ag L-1 for OECD, 50% P and 25% P while for both N reductions, the silver concentrations were 0, 10, 25 and 100 µg Ag L-1. Samples for determining the algal density were taken at every 24 h.

Chronostratigraphic framework at sites GeoB14403 and GeoB14414 from the Gela Basin, Sicily Channel

A multi-proxy chronological framework along with sequence-stratigraphic interpretations unveils composite Milankovitch cyclicity in the sedimentary records of the Last GlacialeInterglacial cycle at NE Gela Basin on the Sicilian continental margin. Chronostratigraphic data (including foraminifera-based eco-biostratigraphy and d18O records, tephrochronological markers and 14C AMS radiometric datings) was derived from the shallow-shelf drill sites GeoB14403 (54.6 m recovery) and GeoB14414 (27.5 m), collected with both gravity and drilled MeBo cores in 193 m and 146 m water depth, respectively. The recovered intervals record Marine Isotope Stages and Substages (MIS) from MIS 5 to MIS 1, thus comprising major stratigraphic parts of the progradational deposits that form the last 100-ka depositional sequence. Calibration of shelf sedimentary units with borehole stratigraphies indicates the impact of higher-frequency (20-ka) sea level cycles punctuating this 100-ka cycle. This becomes most evident in the alternation of thick interstadial highstand (HST) wedges and thinner glacial forced-regression (FSST) units mirroring seaward shifts in coastal progradation. Albeit their relatively short-lived depositional phase, these subordinate HST units form the bulk of the 100-ka depositional sequence. Two mechanisms are proposed that likely account for enhanced sediment accumulation ratios (SAR) of up to 200 cm/ka during these intervals: (1) intensified activity of deep and intermediate Levantine Intermediate Water (LIW) associated to the drowning of Mediterranean shelves, and (2) amplified sediment flux along the flooded shelf in response to hyperpycnal plumes that generate through extreme precipitation events during overall arid conditions. Equally, the latter mechanism is thought to be at the origin of undulated features resolved in the acoustic records of MIS 5 Interstadials, which bear a striking resemblance to modern equivalents forming on late-Holocene prodeltas of other Mediterranean shallow-shelf settings.

Auxiliary material and basic geochemical and benthic foraminiferal stable isotope data for the interval bracketing Eocene Thermal Maximum 2 (ETM2) at DSDP Sites 401 and 550 in the northeastern Atlantic Ocean

Ever since its discovery, Eocene Thermal Maximum 2 (ETM2; ~53.7 Ma) has been considered as one of the "little brothers" of the Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) as it displays similar characteristics including abrupt warming, ocean acidification, and biotic shifts. One of the remaining key questions is what effect these lesser climate perturbations had on ocean circulation and ventilation and, ultimately, biotic disruptions. Here we characterize ETM2 sections of the NE Atlantic (Deep Sea Drilling Project Sites 401 and 550) using multispecies benthic foraminiferal stable isotopes, grain size analysis, XRF core scanning, and carbonate content. The magnitude of the carbon isotope excursion (0.85-1.10 per mil) and bottom water warming (2-2.5°C) during ETM2 seems slightly smaller than in South Atlantic records. The comparison of the lateral d13C gradient between the North and South Atlantic reveals that a transient circulation switch took place during ETM2, a similar pattern as observed for the PETM. New grain size and published faunal data support this hypothesis by indicating a reduction in deepwater current velocity. Following ETM2, we record a distinct intensification of bottom water currents influencing Atlantic carbonate accumulation and biotic communities, while a dramatic and persistent clay reduction hints at a weakening of the regional hydrological cycle. Our findings highlight the similarities and differences between the PETM and ETM2. Moreover, the heterogeneity of hyperthermal expression emphasizes the need to specifically characterize each hyperthermal event and its background conditions to minimalize artifacts in global climate and carbonate burial models for the early Paleogene.

Supplementary material: XRF core scanning data, CaCO3 values, foraminiferal carbon and oxygen isotope data, Mg/Ca data, clay mineralogy and helium isotope results

The Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) is associated with abrupt climate change, carbon cycle perturbation, ocean acidification, as well as biogeographic shifts in marine and terrestrial biota that were largely reversed as the climatic transient waned. We report a clear exception to the behavior of the PETM as a reversing climatic transient in the eastern North Atlantic (Deep-Sea Drilling Project Site 401, Bay of Biscay) where the PETM initiates a greatly prolonged environmental change compared to other places on Earth where records exist. The observed environmental perturbation extended well past the d13C recovery phase and up to 650 kyr after the PETM onset according to our extraterrestrial 3He-based age-model. We observe a strong decoupling of planktic foraminiferal d18O and Mg/Ca values during the PETM d13C recovery phase, which in combination with results from helium isotopes and clay mineralogy, suggests that the PETM triggered a hydrologic change in western Europe that increased freshwater flux and the delivery of weathering products to the eastern North Atlantic. This state change persisted long after the carbon-cycle perturbation had stopped. We hypothesize that either long-lived continental drainage patterns were altered by enhanced hydrological cycling induced by the PETM, or alternatively that the climate system in the hinterland area of Site 401 was forced into a new climate state that was not easily reversed in the aftermath of the PETM.

Climate sensitivity across marine domains of life: limits to evolutionary adaptation shape species interactions, supplementary material

Organisms in all domains, Archaea, Bacteria, and Eukarya will respond to climate change with differential vulnerabilities resulting in shifts in species distribution, coexistence, and interactions. The identification of unifying principles of organism functioning across all domains would facilitate a cause and effect understanding of such changes and their implications for ecosystem shifts. For example, the functional specialization of all organisms in limited temperature ranges leads us to ask for unifying functional reasons. Organisms also specialize in either anoxic or various oxygen ranges, with animals and plants depending on high oxygen levels. Here, we identify thermal ranges, heat limits of growth, and critically low (hypoxic) oxygen concentrations as proxies of tolerance in a meta-analysis of data available for marine organisms, with special reference to domain-specific limits. For an explanation of the patterns and differences observed, we define and quantify a proxy for organismic complexity across species from all domains. Rising complexity causes heat (and hypoxia) tolerances to decrease from Archaea to Bacteria to uni- and then multicellular Eukarya. Within and across domains, taxon-specific tolerance limits likely reflect ultimate evolutionary limits of its species to acclimatization and adaptation. We hypothesize that rising taxon-specific complexities in structure and function constrain organisms to narrower environmental ranges. Low complexity as in Archaea and some Bacteria provide life options in extreme environments. In the warmest oceans, temperature maxima reach and will surpass the permanent limits to the existence of multicellular animals, plants and unicellular phytoplankter. Smaller, less complex unicellular Eukarya, Bacteria, and Archaea will thus benefit and predominate even more in a future, warmer, and hypoxic ocean.

Planktic and benthic 14C reservoir ages, calibrated by a suite of 14C plateaus in the glacial-to-deglacial Suigetsu atmospheric 14C record

We here present a compilation of planktic and benthic 14C reservoir ages for the Last Glacial Maximum (LGM) and early deglacial from 11 key sites of global ocean circulation in the Atlantic and Indo-Pacific Ocean. The ages were obtained by 14C plateau tuning, a robust technique to derive both an absolute chronology for marine sediment records and a high-resolution record of changing reservoir/ventilation ages (Delta14C values) for surface and deep waters by comparing the suite of planktic 14C plateaus of a sediment record with that of the atmospheric 14C record (Sarnthein et al., 2007, doi:10.1029/173GM13). Results published thus far used as atmospheric 14C reference U/Th-dated corals, the Cariaco planktic record, and speleothems (Fairbanks et al., 2005, doi:10.1016/j.quascirev.2005.04.007; Hughen et al., 2006, doi:10.1016/j.quascirev.2006.03.014; Beck et al., 2001, doi:10.1023/A:1008175728826). We have now used the varve-counted atmospheric 14C record of Lake Suigetsu terrestrial macrofossils (Ramsey et al., 2012, doi:10.1126/science.1226660) to recalibrate the boundary ages and reservoir ages of the seven published records directly to an atmospheric 14C record. In addition, the results for four new cores and further planktic results for four published records are given. Main conclusions from the new compilation are: (1) The Suigetsu atmospheric 14C record on its varve counted time scale reflects all 14C plateaus, their internal structures and relative length previously identified, but implies a rise in the average 14C plateau age by 200-700 14C yr during LGM and early deglacial times. (2) Based on different 14C ages of coeval atmospheric and planktic 14C plateaus, marine surface water Delta14C may have temporarily dropped to an equivalent of ~0 yr in low-latitude lagoon waters, but reached >2500 14C yr both in stratified subpolar waters and in upwelled waters such as in the South China Sea. These values differ significantly from a widely assumed constant global planktic Delta14C value of 400 yr. (3) Suites of deglacial planktic Delta14C values are closely reproducible in 14C records measured at neighboring core sites. (4) Apparent deep-water 14C ventilation ages (equivalents of benthic Delta14C), deduced from the sum of planktic Delta14C and coeval benthic-planktic 14C differences, vary from 500 up to >5000 yr in LGM and deglacial ocean basins.

Mineralogical, geochemical, and lipid biomarker study of cabonate precipitates at station GeoB9908-1

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low d13C values measured on carbonates (-41 to -32 per mill V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. d18O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly 18O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.