CaCO3, foraminifer fragmentation, benthic carbon isotopes, coarse lithic counts and radiogenic isotopes (Sr, Nd, Pb) of the Pliocene and earliest Pleistocene terrigenous component (3.3-2.4 Ma) of IODP Site 306-U1313

We present Plio-Pleistocene records of sediment color, %CaCO3, foraminifer fragmentation, benthic carbon isotopes (d13C) and radiogenic isotopes (Sr, Nd, Pb) of the terrigenous component from IODP Site U1313, a reoccupation of benchmark subtropical North Atlantic Ocean DSDP Site 607. We show that (inter)glacial cycles in sediment color and %CaCO3 pre-date major northern hemisphere glaciation and are unambiguously and consistently correlated to benthic oxygen isotopes back to 3.3 million years ago (Ma) and intermittently so probably back to the Miocene/Pliocene boundary. We show these lithological cycles to be driven by enhanced glacial fluxes of terrigenous material (eolian dust), not carbonate dissolution (the classic interpretation). Our radiogenic isotope data indicate a North American source for this dust (~3.3-2.4 Ma) in keeping with the interpreted source of terrestrial plant wax-derived biomarkers deposited at Site U1313. Yet our data indicate a mid latitude provenance regardless of (inter)glacial state, a finding that is inconsistent with the biomarker-inferred importance of glaciogenic mechanisms of dust production and transport. Moreover, we find that the relation between the biomarker and lithogenic components of dust accumulation is distinctly non-linear. Both records show a jump in glacial rates of accumulation from Marine Isotope Stage, MIS, G6 (2.72 Ma) onwards but the amplitude of this signal is about 3-8 times greater for biomarkers than for dust and particularly extreme during MIS 100 (2.52 Ma). We conclude that North America shifted abruptly to a distinctly more arid glacial regime from MIS G6, but major shifts in glacial North American vegetation biomes and regional wind fields (exacerbated by the growth of a large Laurentide Ice Sheet during MIS 100) likely explain amplification of this signal in the biomarker records. Our findings are consistent with wetter-than-modern reconstructions of North American continental climate under the warm high CO2 conditions of the Early Pliocene but contrast with most model predictions for the response of the hydrological cycle to anthropogenic warming over the coming 50 years (poleward expansion of the subtropical dry zones).

Composition of ferromanganese crusts from the Atlantic, Pacific and Indian Oceans

A collection of layered ferromanganese ores (27 samples) from the Atlantic and Pacific oceans was studied. Trace element and PGE contents were determined layer-by-layer (up to 10 microlayers) in 13 of these samples. The trace, rare earth, and platinum group element distributions, including their layer-to-layer variations, were compared in hydrogenic and hydrothermal crusts from different regions. It was found that the main PGE variations (by a factor of 10-50) are related to their layer-to-layer variations within a given ore field. The distributions of PGE and trace elements are strongly heterogeneous, which is related, first, to different contents of the elements in the layers of different age in ferromanganese crusts (FMC) and, second, to the observed regional heterogeneity and influence of hydrothermal fluids. Geochemical data indicate that CFC formation was mainly caused by the hydrochemical precipitation of material from seawater. This process was accompanied by diagenetic phenomena, water-rock interaction, and influence of volcanic and hydrothermal sources.

Petrology and geochemistry of basalts from the Vavilov Basin

During ODP Leg 107, two holes were drilled in the basement of Vavilov Basin, a central oceanic area of the Tyrrhenian sea. Hole 655B is located near the Gortani ridge in off-axis position at the western rim of the basin; Hole 651A is located on a basement swell at the axis of the basin. This paper deals with mineral chemistry, major and trace element geochemistry, and petrogenesis of the basalts recovered in the two holes. The mineralogy of the basalts is broadly homogeneous, but all of them have suffered important seawater alteration. Their major-element compositions are similar to both normal-mid-ocean-ridge-basalts (N-MORB) and back-arc-basalts (BAB) except for Na2O contents (BAB-like), and K2O which is somewhat enriched in upper unit of Hole 651 A. Their affinity with N-MORB and BAB is confirmed by using immobile trace elements such as Zr, Y, and Nb. However, basalts from the two sites present contrasting geochemical characteristics on spidergrams using incompatible elements. Hole 655B basalts are homogeneous enriched tholeiites, similar to those from DSDP Hole 373 (located on the opposite side of the basin near the eastern rim), and show affinities with enriched MORB (E-MORB). At Hole 651 A, the two basalt units are chemically distinct. One sample recovered in lower unit is rather similar to those from Hole 655B, but basalts from upper unit display calc-alkaline characteristic evidenced by the increase of light-ion-lithophile-element (LILE)/high-field-strength-element (HFSE) ratio, and appearance of a negative Nb-anomaly, making them comparable with orogenic lavas from the adjacent Eolian arc. The observed chemical compositions of the basalts are consistent with a derivation of the magmas from a N-MORB type source progressively contaminated by LILE-enriched fluids released from dehydration of the bordering subducted plate. Implications for evolution of the Tyrrhenian basin are tentatively proposed taking into consideration geochemical and chronological relationships between basalts from Leg 107 Holes 655B and 651 A, together with data from Leg 42 Site 373 and Vavilov Seamount. These data illustrate back-arc spreading in ensialic basin closely associated with the maturation of the adjacent subduction, followed by the growth of late off-axis central volcano, whereas the active subduction retreats southeastward.

40-year long monthly-resolved Sr/Ca record from 2.35 ka Bonaire coral, sample BON-6-A

We present a 40-year long monthly resolved Sr/Ca record from a fossil Diploria strigosa coral from Bonaire (Southern Caribbean Sea) dated with U/Th at 2.35 ka before present (BP). Secondary modifiers of this sea surface temperature (SST) proxy in annually-banded corals such as diagenetic alteration of the skeleton and skeletal growth-rate are investigated. Extensive diagenetic investigations reveal that this fossil coral skeleton is pristine which is further supported by clear annual cycles in the coral Sr/Ca record. No significant correlation between annual growth rate and Sr/Ca is observed, suggesting that the Sr/Ca record is not affected by coral growth. Therefore, we conclude that the observed interannual Sr/Ca variability was influenced by ambient SST variability. Spectral analysis of the annual mean Sr/Ca record reveals a dominant frequency centred at 6-7 years that is not associated with changes of the annual growth rate. The first monthly resolved coral Sr/Ca record from the Southern Caribbean Sea for preindustrial time suggests that fossil corals from Bonaire are suitable tools for reconstructing past SST variability. Coastal deposits on Bonaire provide abundant fossil D. strigosa colonies of Holocene age that can be accurately dated and used to reconstruct climate variability. Comparisons of long monthly resolved Sr/Ca records from multiple fossil corals will provide a mean to estimate seasonality and interannual to interdecadal SST variability of the Southern Caribbean Sea during the Holocene.

Strong shift from HCO3- to CO2 uptake in Emiliania huxleyi with acidification: new approach unravels acclimation versus short-term pH effects

Effects of ocean acidification on Emiliania huxleyi strain RCC 1216 (calcifying, diploid life-cycle stage) and RCC 1217 (non-calcifying, haploid life-cycle stage) were investigated by measuring growth, elemental composition, and production rates under different pCO2 levels (380 and 950 µatm). In these differently acclimated cells, the photosynthetic carbon source was assessed by a (14)C disequilibrium assay, conducted over a range of ecologically relevant pH values (7.9-8.7). In agreement with previous studies, we observed decreased calcification and stimulated biomass production in diploid cells under high pCO2, but no CO2-dependent changes in biomass production for haploid cells. In both life-cycle stages, the relative contributions of CO2 and HCO3 (-) uptake depended strongly on the assay pH. At pH values =< 8.1, cells preferentially used CO2 (>= 90 % CO2), whereas at pH values >= 8.3, cells progressively increased the fraction of HCO3 (-) uptake (~45 % CO2 at pH 8.7 in diploid cells; ~55 % CO2 at pH 8.5 in haploid cells). In contrast to the short-term effect of the assay pH, the pCO2 acclimation history had no significant effect on the carbon uptake behavior. A numerical sensitivity study confirmed that the pH-modification in the (14)C disequilibrium method yields reliable results, provided that model parameters (e.g., pH, temperature) are kept within typical measurement uncertainties. Our results demonstrate a high plasticity of E. huxleyi to rapidly adjust carbon acquisition to the external carbon supply and/or pH, and provide an explanation for the paradoxical observation of high CO2 sensitivity despite the apparently high HCO3 (-) usage seen in previous studies.

Fast coral reef calcifiers are more sensitive to ocean acidification in short-term laboratory incubations

To identify the properties of taxa sensitive and resistant to ocean acidification (OA), we tested the hypothesis that coral reef calcifiers differ in their sensitivity to OA as predictable outcomes of functional group alliances determined by conspicuous traits. We contrasted functional groups of eight corals and eight calcifying algae defined by morphology in corals and algae, skeletal structure in corals, spatial location of calcification in algae, and growth rate in corals and algae. The responses of calcification to OA were unrelated to morphology and skeletal structure in corals; they were, however, affected by growth rate in corals and algae (fast calcifiers were more sensitive than slow calcifiers), and by the site of calcification and morphology in algae. Species assemblages characterized by fast growth, and for algae, also cell-wall calcification, are likely to be ecological losers in the future ocean. This shift in relative success will affect the relative and absolute species abundances as well as the goods and services provided by coral reefs.

Elevated CO2 levels do not affect the shell structure of the bivalve Arctica islandica from the western Baltic

Shells of the bivalve Arctica islandica are used to reconstruct paleo-environmental conditions (e.g. temperature) via biogeochemical proxies, i.e. biogenic components that are related closely to environmental parameters at the time of shell formation. Several studies have shown that proxies like element and isotope-ratios can be affected by shell growth and microstructure. Thus it is essential to evaluate the impact of changing environmental parameters such as high pCO2 and consequent changes in carbonate chemistry on shell properties to validate these biogeochemical proxies for a wider range of environmental conditions. Growth experiments with Arctica islandica from the Western Baltic Sea kept under different pCO2 levels (from 380 to 1120 µatm) indicate no affect of elevated pCO2 on shell growth or crystal microstructure, indicating that A. islandica shows an adaptation to a wider range of pCO2 levels than reported for other species. Accordingly, proxy information derived from A. islandica shells of this region contains no pCO2 related bias.

Dissolved iron measurements from 32 stations in the Central Arctic Ocean and Arctic Shelf Sea during POLARSTERN expedition ARK-XXII/2

Concentrations of dissolved (<0.2 µm) Fe (DFe) in the Arctic shelf seas and in the surface waters of the central Arctic Ocean are presented. In the Barents and Kara seas, near-surface DFe minima indicate depletion of DFe by phytoplankton growth. Below the surface, lower DFe concentrations in the Kara Sea (~0.4-0.6 nM) than in the Barents Sea (~0.6-0.8 nM) likely reflect scavenging removal or biological depletion of DFe. Very high DFe concentrations (>10 nM) in the bottom waters of the Laptev Sea shelf may be attributed to either sediment resuspension, sinking of brine or regeneration of DFe in the lower layers. A significant correlation (R2 = 0.60) between salinity and DFe is observed. Using d18O, salinity, nutrients and total alkalinity data, the main source for the high (>2 nM) DFe concentrations in the Amundsen and Makarov Basins is identified as (Eurasian) river water, transported with the Transpolar Drift (TPD). On the North American side of the TPD, the DFe concentrations are low (<0.8 nM) and variations are determined by the effects of sea-ice meltwater, biological depletion and remineralization and scavenging in halocline waters from the shelf. This distribution pattern of DFe is also supported by the ratio between unfiltered and dissolved Fe (high (>4) above the shelf and low (<4) off the shelf).

Vertical distribution of zooplankton biomass in the Sea of Japan at Station VITYAZ7519

Vertical distribution of common zooplankton species is examined on the base of two series of layer-by-layer net catches down to depth of 3400 m. Differences between the series are significant for most species only near the surface, whereas in deeper layers character of distribution remains the same. Great depths in the Sea of Japan are populated most actively by species performing intensive daily migrations, and less actively by species continuously confined to a definite depth range. Different character of nutrition of the animals apparently determines extent of utilization of deep layers, which are usual for the species.

(Table 1) Biomass of plankton in the Sea of Japan at Station VITYAZ6674

Vertical distribution of zooplankton biomass from the surface to bottom layers (3400 m) is examined. Material was collected layer by layer by a BR 113/140 net at 41°59' N and 133°37' E on July 2 and 3, 1970. Quantity of plankton below 1000 m was found to be much less than at corresponding depths in the adjacent regions of the ocean. This impoverishment is due to absence of oceanic bathypelagic animals in deep layers of the Sea of Japan. Absence of specialized predators (plankton-feeders) deep in the Sea of Japan results in underconsumption of interzonal animals that sink to great depths. Upon dying they should reach the floor in larger quantities than in the ocean.

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

(Figure 2) Stratigraphic distribution of Schizosphaerella in DSDP Hole 79-547B

The Jurassic (hemi)pelagic continental margin deposits drilled at Hole 547B, off the Moroccan coast, reveal striking Tethyan affinity. Analogies concern not only types and gross vertical evolution of facies, but also composition and textures of the fine sediment and the pattern of diagenetic alteration. In this context, the occurrence of the nanno-organism Schizosphaerella Deflandre and Dangeard (sometimes as a conspicuous portion of the fine-grained carbonate fraction) is of particular interest. Schizosphaerella, an incertae sedis taxon, has been widely recorded as a sediment contributor from Tethyan Jurassic deeper-water carbonate facies exposed on land. Because of its extremely long range (Hettangian to early Kimmeridgian), the genus Schizosphaerella (two species currently described, S. punctulata Deflandre and Dangeard and S. astrea Moshkovitz) is obviously not of great biostratigraphic interest. However, it is of interest in sedimentology and petrology. Specifically, Schizosphaerella was often the only component of the initial fine-grained fraction of a sediment that was able to resist diagenetic obliteration. However, alteration of the original skeletal structure did occur to various degrees. Crystal habit and mineralogy of the fundamental skeletal elements, as well as their mode of mutual arrangement in the test wall with the implied high initial porosity of the skeleton (60-70%), appear to be responsible for this outstanding resistance. Moreover, the ability to concentrate within and, in the case of the species S. punctulata, around the skeleton, large amounts of diagenetic calcite also contributed to the resistance. In both species of Schizosphaerella, occlusion of the original skeletal void space during diagenesis appears to have proceeded in an analogous manner, with an initial slight uniform syntaxial enlargement of the basic lamellar skeletal crystallites followed, upon mutual impingement, by uneven accretion of overgrowth cement in the remaining skeletal voids. However, distinctive fabrics are evident according to the different primary test wall architecture. In S. punctulata, intraskeletal cementation is usually followed by the growth of a radially structured crust of bladed to fibrous calcite around the valves. These crusts are interpreted as a product of aggrading neomorphism, associated with mineralogic stabilization of the original, presumably polyphase, sediment. Data from Hole 547B, along with inferences, drawn from the fabric relationships, suggest that the crusts formed and (inferentially) mineralogic stabilization occurred at a relatively early time in the diagenetic history in the shallow burial realm. An enhanced rate of lithification at relatively shallow burial depths and thus the chance for neomorphism to significantly influence the textural evolution of the buried sediment may be related to a lower Mg/Ca concentration ratio in the oceanic system and, hence, in marine pore waters in pre-Late Jurassic times.

Calcification repsonse of m,arione bivalves to changed carbonate chemistry

Bivalve calcification, particularly of the early larval stages, is highly sensitive to the change in ocean carbonate chemistry resulting from atmospheric CO2 uptake. Earlier studies suggested that declining seawater [CO32-] and thereby lowered carbonate saturation affect shell production. However, disturbances of physiological processes such as acid-base regulation by adverse seawater pCO2 and pH can affect calcification in a secondary fashion. In order to determine the exact carbonate system component by which growth and calcification are affected it is necessary to utilize more complex carbonate chemistry manipulations. As single factors, pCO2 had no effects and [HCO3-] and pH had only limited effects on shell growth, while lowered [CO32-] strongly impacted calcification. Dissolved inorganic carbon (CT) limiting conditions led to strong reductions in calcification, despite high [CO32-], indicating that [HCO3-] rather than [CO32-] is the inorganic carbon source utilized for calcification by mytilid mussels. However, as the ratio [HCO3-] / [H+] is linearly correlated with [CO32-] it is not possible to differentiate between these under natural seawater conditions. An equivalent of about 80 µmol kg-1 [CO32-] is required to saturate inorganic carbon supply for calcification in bivalves. Below this threshold biomineralization rates rapidly decline. A comparison of literature data available for larvae and juvenile mussels and oysters originating from habitats differing substantially with respect to prevailing carbonate chemistry conditions revealed similar response curves. This suggests that the mechanisms which determine sensitivity of calcification in this group are highly conserved. The higher sensitivity of larval calcification seems to primarily result from the much higher relative calcification rates in early life stages. In order to reveal and understand the mechanisms that limit or facilitate adaptation to future ocean acidification, it is necessary to better understand the physiological processes and their underlying genetics that govern inorganic carbon assimilation for calcification.