ALBERT

Description: Brachiopod shells are widely used as an archive to reconstruct elemental and isotopic composition of seawater. Studies, focused on oxygen and carbon isotopes over the last decades, are increasingly extending to the emerging calcium isotope system. To date, only little attention has been paid to test the reliability of fossil brachiopods on their modern counterparts. In this context, the present study investigates two modern brachiopods, Terebratulina septentrionalis (eastern Canada, 5–30 m depth, 7.1 °C seasonal temperature variation, two-layer shell) and Gryphus vitreus (northern Mediterranean, 200 m depth, constant all-year round temperature, three-layer shell). Both species were sampled along the ontogenetic growth direction and calcium, oxygen, and carbon isotopes as well as elemental concentration were measured. Calcium isotopes were analyzed on TIMS. The elemental composition was analyzed by LA-ICP-MS and ICP-AES. The results indicate an intra-specimen δ44/40Ca variation ranging from 0.16 to 0.33‰, pointing to a fairly homogenous distribution of calcium isotopes in brachiopod shells. However, in the light of the suggested 0.7‰ increase in calcium isotopes over the Phanerozoic such intra-specimen variations constrain ocean reconstruction. δ44/40Ca values of T. septentrionalis do not seem to be affected by growth rate. Calcium isotopic values of G. vitreus are heavy in the central part of the shell and trend towards lighter values in peripheral areas approaching the maximum isotopic composition of T. septentrionalis. The maximum inter-species δ44/40Ca difference of 0.62‰ between T. septentrionalis and G. vitreus indicates that care should be taken when using different taxa, species with different strontium content or brachiopods with specialized shell structure, such as G. vitreus, for ocean water reconstruction in terms of Ca isotopic composition. T. septentrionalis may record Ca isotopic fractionation related to seasonal seawater temperature variations in its shell but this is difficult to resolve at the current analytical precision. Average δ18O-derived temperatures of the two investigated species are close to on-site measured temperatures.

Description: Fossil corals are unique archives of past seasonal climate variability, providing vital information about seasonal climate phenomena such as ENSO and monsoons. However, submarine diagenetic processes can potentially obscure the original climate signals and lead to false interpretations. Here we demonstrate the potential of laser ablation ICP-MS to rapidly detect secondary aragonite precipitates in fossil Porites colonies recovered by Integrated Ocean Drilling Program (IODP) Expedition 310 from submerged deglacial reefs off Tahiti. High resolution (100 μm) measurements of coralline B/Ca, Mg/Ca, S/Ca, and U/Ca ratios are used to distinguish areas of pristine skeleton from those afflicted with secondary aragonite. Measurements of coralline Sr/Ca, U/Ca and oxygen isotope ratios, from areas identified as pristine, reveal that the seasonal range of sea surface temperature in the tropical south Pacific during the last deglaciation (14.7 and 11 ka) was similar to that of today.

Description: High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (View the MathML sourceSO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate–methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, ‘relict’ barite fronts would only be preserved for a few thousands of years, if at all.

Description: The Mid-Atlantic Ridge between the Ascension and Bode Verde Fracture Zones exhibits anomalous crustal thickness and geochemical compositions, which could reflect the presence of either small, enriched heterogeneities in the upper mantle or a weak, diffuse mantle plume. We report new trace element (106 samples) and Sr, Nd and Pb (double spike) isotope data from 72 ridge axis samples and 9 off-axis seamount samples between 5 and 11°S, aswell asU–Th–Ra disequilibria data for the seamounts. The U-series data constrain the age of one sample from Seamount D, furthest (120 km) east of the shallowest part of the ridge, to be b10,000 yrs old and the samples from the other three seamounts closer to the ridge to be younger than 240,000 yrs. As can be most clearly discerned on a diagram of 208Pb/206Pb vs. 143Nd/144Nd, at least four distinct components are required to explain the geochemical variations along the ridge: 1) a common depleted (D-MORBlike) component in samples near and north of the Ascension Fracture Zone (4.8–7.6°S), representing the most depleted compositions sampled thus far along the mid-Atlantic ridge, 2) an enriched component upwelling beneath Ascension Island and the northern A1 ridge segment (segment numbers increase from A1 to A4 going south from the Ascension Fracture Zone), 3) an enriched component upwelling beneath the A2 ridge segment, and 4) an enriched component upwelling beneath the line of seamounts east of the A3 segment and the A3 and A4 segments. The A1 and the A3+A4 segment lavas form well-defined mixing arrays, which extend from Ascension Island and the A3 seamounts respectively to the depleted D-MORB component, interpreted to reflect local ambient mantle. We propose that the enriched components represent different packages of subducted ocean crust and/or ocean island basalt (OIB) type volcanic islands and seamounts that have either been recycled through 1) the shallowmantle, upwelling passively beneath the ridge systemor 2) the deep mantle via an actively upwelling heterogeneous mantle plume that interacts with the ridge system.

Description: Barrow, the northernmost point in Alaska, is one of the most intensively studied areas in the Arctic. However, paleoenvironmental evidence is limited for northern Alaska for the Lateglacial-Holocene transition. For a regional paleoenvironmental reconstruction, we investigated a permafrost ice-wedge tunnel near Barrow, Alaska. The studied site was first excavated in the early 1960s and intercepts a buried ice-wedge system at 3e6 m depth below the surface. A multi-methodological approach was applied to this buried ice-wedge system and the enclosing sediments, which in their combination, give new insight into the Late Quaternary environmental and climate history. Results of geochronological, sedimentological, cryolithological, paleoecological, isotope geochemical and microbiological studies reflect different stages of mid to late Wisconsin (MW to LW), Allerød (AD), Younger Dryas (YD), Preboreal (PB), and Late Holocene paleoenvironmental evolution. The LWage of the site is indicated by AMS dates in the surrounding sediments of 21.7 kyr BP at the lateral contact of the ice-wedge system as well as 39.5 kyr BP below the ice-wedge system. It is only recently that in this region, stable isotope techniques have been employed, i.e. to characterize different types of ground ice. The stable isotope record (oxygen: δ18O; hydrogen: δD) of two intersecting ice wedges suggests different phases of the northern Alaskan climate history from AD to PB, with radiocarbon dates from 12.4 to 9.9 kyr BP (ranging from 14.8 to 10.6 kyr cal BP). Stable isotope geochemistry of ice wedges reveals winter temperature variations of the Lateglacial-Holocene transition including a prominent YD cold period, clearly separated from the warmer AD and PB phases. YD is only weakly developed in summer temperature indicators (such as pollen) for the northern Alaska area, and by consequence, the YD cold stadial was here especially related to the winter season. This highlights that the combination of winter and summer indicators comprehensively describes the seasonality of climate-relevant processes in discrete time intervals. The stable isotope record for the Barrow buried ice-wedge system documents for the first time winter climate change at the Lateglacial-Holocene transition continuously and at relatively high (likely centennial) resolution.

Description: The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (δ44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the δ44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of δ44/40Ca ranges from 0.6 to 0.1‰, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and δ44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by δ18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's δ44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean. Highlights ► Corals cultured in aquaria or from natural environment show the same Ca isotopic composition. ► δ44/40Ca of coral skeleton is independent of depositional setting environment. ► Strong influence of vital effects on coral skeleton δ44/40Ca composition and calcification mechanisms

Description: Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area (“Batumi seep area”) located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in δ18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Description: Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70–80% and up to 30% of C2–C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200–400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Description: Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone. Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (〉 99.85 mol.% of ∑[C1–C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] 〉 1000) and stable isotopic compositions of methane (δ13C = − 53.5‰ V-PDB; D/H around − 175‰ SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by 〉 0.03 mol.% (∑[C1–C4, CO2]) relative to the other gas types and the virtual lack of 14C–CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely. As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C1–C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C–CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.

Description: In their article, Geyer and Martí (2010) propose that the evolution and origin of the volcanic islands which constitute the Canarian archipelago are strongly controlled by regional tectonic “Atlantic” and “African” structures. In their Fig. 1a they sketch the geometry of the Iberian and Moroccan microplates and the respective boundary zones with respect to Africa (Nubia) and Eurasia (Mantovani et al., 2007). Dashed lines indicating presumed plate boundaries cross the Canarian archipelago, which will therefore be located along a lithospheric fracture, the boundary between the Moroccan and African (Nubia) microplates. This regional fracture extends from the Atlas to the Atlantis fracture zone, coinciding in parts with the propagating fracture postulated by Anguita and Hernán (1975). In Fig. 1b of Geyer and Martí (2010), dashed lines indicate the orientation of the most evident tectonic structures visible on the ocean floor. As we show in this comment, all of these mapped “faults” are artifacts.