Stable oxygen and carbon isotope compositions of Campanian grainstones and rudstones

Petrographic descriptions and stable oxygen and carbon isotope compositions of microsamples of Campanian-age sediment gravity-flow deposits from Northeast Providence Channel, Bahamas, indicate deep-marine cementation of shallow-marine skeletal grains that were transported to the channel during the Late Cretaceous. Shallow-marine components are represented by mollusks, especially rudists, and shallow-water benthic foraminifers as well as sparse echinoderm and algal grains. The sole evidence of diagenesis in shallow-marine environments consists of micrite envelopes around skeletal grains. Shallow-marine skeletal grains have mean stable isotope values of -3.1 per mil d18O and +2.6 per mil d13C. The d18O values are consistent with precipitation in equilibrium with warm (20°-30°C), shallow-marine water. Deep-marine components are represented by equant calcite spar cements and rip-up clasts of slope sediments. Spar cements, exhibiting hexagonal morphology with scalenohedral terminations, most commonly occur as thin isopachous linings in the abundant porosity. Deep-marine cements have mean stable isotope values of - 1.1 per mil d18O and +2.7 per mil d13C. Deep-marine cements are 18O-enriched relative to shallow-marine skeletal grains, consistent with precipitation in equilibrium with colder (10°-20°C), deep-marine waters. The cement .source during lithification appears to have been dissolution of aragonite and high-magnesium calcite skeletal grains, which made up part of the transported sediment. Interbedded periplatform ooze remains uncemented, or poorly cemented, probably because of lower permeability. Equant spar cements that occur in gravity-flow deposits recovered from Hole 634A have stable isotope compositions similar to spars in Lower and mid-Cretaceous shallow-water limestones exposed on the Bahama Escarpment, to Campanian-Paleocene deep-marine hardgrounds recovered during DSDP Leg 15 in the Caribbean, and to spars in Aptian-Albian talus deposits at the base of the Campeche Escarpment recovered during DSDP Leg 77.

Stable isotope composition of carbonate components of Rhaetian shallow-water limestones of the Wombat Plateau

Stable oxygen- and carbon-isotope ratios of Rhaetian (upper Triassic) limestone samples from the Wombat Plateau, northwest Australia, were measured to explore possible diagenetic pathways that the material underwent after deposition in a shallow-water environment, before plateau submergence in the Early Cretaceous. Host sediment isotopic values cluster near typical marine carbonate values (d18O ranging from -2.57 per mil to +1.78 per mil and d13C, from +2.45 per mil to +4.01 per mil). Isotopic values of equant clear calcite lining or filling rock pores also plot in the field of marine cements (d18O = +1.59 per mil to -2.24 per mil and d13C = +4.25 per mil to +2.57 per mil), while isotopic values for neomorphic calcites replacing skeletal (megalodontid shell) carbonate material show a wider scatter of oxygen and carbon values, d18O ranging from +2.73 per milo to -6.2 per mil and d13C, from +5.04 per mil to +1.22 per mil. Selective dissolution of metastable carbonate phases (aragonite?) and neomorphic replacement of skeletal material probably occurred in a meteoric phreatic environment, although replacement products (inclusion-rich microspar, clear neomorphic spar, etc.) retained the original marine isotopic signature because transformation probably occurred in a closed system dominated by the composition of the dissolving phases (high rock/water ratio). The precipitation of late-stage equant (low-Mg?) calcite cement in the pores occurred in the presence of normal marine waters, probably in a deep-water environment, after plateau drowning. Covariance of d18O and d13C toward negative values indeed suggests influence of meteorically modified fluids. However, none of the samples shows negative carbon values, excluding the persistence of organic-rich soils on subaerial karstic surfaces (Caribbean-style diagenesis). Petrographical and geochemical data are consistent with the sedimentological evidence of plateau drowning in post-Rhaetian times and with a submarine origin of the >70-m.y.-long Jurassic hiatus.

Geochemistry of sediments from the mid-oceanic Kolbeinsey Ridge

In order to assess recent submarine volcanic contributions to the sediments from the active Kolbeinsey Ridge, surface samples were analyzed chemically. The contribution of major and trace elements studied differ within the study area. A statistical analysis of the geochemical variables using factor analysis and cluster method allows to distinguish possible sample groups. Cluster method identifies three distinct sediment groups located in different areas of sedimentation. Group 1 is characterized by highest contents of Fe2O3, V, Co, Ni, Cu and Zn demonstrating the input of volcaniclastic material. Group 2 comprises high values of CaCO3, CaO and Sr representing biogenic carbonate. Group 3 is characterized by the elements K, Rb, Cs, La and Pb indicating the terrigenous component. The absolute percentage of the volcanic, biogenic and terrigenous components in the bulk sediments was calculated by using a normative sediment method. The highest volcanic component (> 60% on a carbonate free basis) is found on the ridge crest. The biogenic component is highest (10-30%) in the eastern part of the Spar Fracture Zone influenced by the East Iceland Current. Samples from the western and southeastern region of the study area contain more than 90% of terrigenous component which appears to be mainly controlled by input of ice-rafted debris.

Animation of micro-computed tomography of bioerosion trace Entobia megastoma made by East Australian bioeroding sponge Cliona celata

Endolithic bioerosion is difficult to analyse and to describe, and it usually requires damaging of the sample material. Sponge erosion (Entobia) may be one of the most difficult to evaluate as it is simultaneously macroscopically inhomogeneous and microstructurally intricate. We studied the bioerosion traces of the two Australian sponges Cliona celata Grant, 1826 (sensu Schönberg 2000) and Cliona orientalis Thiele, 1900 with a newly available radiographic technology: high resolution X-ray micro-computed tomography (MCT). MCT allows non-destructive visualisation of live and dead structures in three dimensions and was compared to traditional microscopic methods. MCT and microscopy showed that C. celata bioerosion was more intense in the centre and branched out in the periphery. In contrast, C. orientalis produced a dense, even trace meshwork and caused an overall more intense erosion pattern than C. celata. Extended pioneering filaments were not usually found at the margins of the studied sponge erosion, but branches ended abruptly or tapered to points. Results obtained with MCT were similar in quality to observations from transparent optical spar under the dissecting microscope. Microstructures could not be resolved as well as with e.g. scanning electron microscopy (SEM). Even though sponge scars and sponge chips were easily recognisable on maximum magnification MCT images, they lacked the detail that is available from SEM. Other drawbacks of MCT involve high costs and presently limited access. Even though MCT cannot presently replace traditional techniques such as corrosion casts viewed by SEM, we obtained valuable information. Especially for the possibility to measure endolithic pore volumes, we regard MCT as a very promising tool that will continue to be optimised. A combination of different methods will produce the best results in the study of Entobia.

Geochemistry of carbonate cements of ODP Leg 112 samples

The evolution of pore fluids migrating through the forearc basins, continental massif, and accretionary prism of the Peru margin is recorded in the sequence of carbonate cements filling intergranular and fracture porosities. Petrographic, mineralogic, and isotopic analyses were obtained from cemented clastic sediments and tectonic breccias recovered during Leg 112 drilling. Microbial decomposition of the organic-rich upwelling facies occurs during early marine diagenesis, initially by sulfate-reduction mechanisms in the shallow subsurface, succeeded by carbonate reduction at depth. Microcrystalline, authigenic cements formed in the sulfate-reduction zone are 13C-depleted (to -20.1 per mil PDB), and those formed in the carbonate-reduction zone are 13C-enriched (to +19.0 per mil PDB). Calcium-rich dolomites and near-stoichiometric dolomites having uniformly heavy d18O values (+2.7 to +6.6 per mil PDB) are typical organic decomposition products. Quaternary marine dolomites from continental-shelf environments exhibit the strongest sulfate-reduction signatures, suggesting that Pleistocene sea-level fluctuations created a more oxygenated water column, caused periodic winnowing of the sediment floor, and expanded the subsurface penetration of marine sulfate. We have tentatively identified four exotic cement types precipitated from advected fluids and derived from the following diagenetic environments: (1) meteoric recharge, (2) basalt alteration, (3) seafloor venting and (4) hypersaline concentration. Coarsely crystalline, low-magnesium (Lo-Mg) calcite cements having pendant and blocky-spar morphologies, extremely negative d18O values (to -7.5 per mil PDB), and intermediate d13C values (-0.4 per mil to +4.6 per mil PDB) are found in shallow-marine Eocene strata. These cements are evidently products of meteoric diagenesis following subaerial emergence during late Eocene orogenic movements, although the strata have since subsided to greater than 4,000 m below sea level. Lo-Mg calcite cements filling scaly fabrics in the late Miocene accretionary prism sediments are apparently derived from fluids having lowered magnesium/calcium (Mg/Ca) and 18O/16O ratios; such fluids may have reacted with the subducting oceanic crust and ascended through the forearc along shallow-dipping thrust faults. Micritic, high-magnesium (Hi-Mg) calcite cements having extremely depleted d13C values (to -37.3%c PDB), and a benthic fauna of giant clams (Calyptogena sp.) supported by a symbiotic, chemoautotrophic metabolism, provide evidence for venting of methane-charged waters at the seafloor. Enriched d18O values (to +6.6%c PDB) in micritic dolomites from the continental shelf may be derived from hypersaline fluids that were concentrated in restricted lagoons behind an outer-shelf basement ridge, reactivated during late Miocene orogenesis.

Stable isotope analysis and biomarkers of carbonates from the Columbia River in southwestern Washington, USA

Exotic limestone masses with silicified fossils, enclosed within deep-water marine siliciclastic sediments of the Early to Middle Miocene Astoria Formation, are exposed along the north shore of the Columbia River in southwestern Washington, USA. Samples from four localities were studied to clarify the origin and diagenesis of these limestone deposits. The bioturbated and reworked limestones contain a faunal assemblage resembling that of modern and Cenozoic deep-water methane-seeps. Five phases make up the paragenetic sequence: (1) micrite and microspar; (2) fibrous, banded and botryoidal aragonite cement, partially replaced by silica or recrystallized to calcite; (3) yellow calcite; (4) quartz replacing carbonate phases and quartz cement; and (5) equant calcite spar and pseudospar. Layers of pyrite frequently separate different carbonate phases and generations, indicating periods of corrosion. Negative d13Ccarbonate values as low as -37.6 per mill V-PDB reveal an uptake of methane-derived carbon. In other cases, d13Ccarbonate values as high as 7.1 per mill point to a residual, 13C-enriched carbon pool affected by methanogenesis. Lipid biomarkers include 13C-depleted, archaeal 2,6,10,15,19-pentamethylicosane (PMI; d13C: -128 per mill), crocetane and phytane, as well as various iso- and anteiso-carbon chains, most likely derived from sulphate-reducing bacteria. The biomarker inventory proves that the majority of the carbonates formed as a consequence of sulphate-dependent anaerobic oxidation of methane. Silicification of fossils and early diagenetic carbonate cements as well as the precipitation of quartz cement - also observed in other methane-seep limestones enclosed in sediments with abundant diatoms or radiolarians - is a consequence of a preceding increase of alkalinity due to anaerobic oxidation of methane, inducing the dissolution of silica skeletons. Once anaerobic oxidation of methane has ceased, the pH drops again and silica phases can precipitate.

The formation of a subsurface anticyclonic eddy in the Peru-Chile Undercurrent and its impact on the near-coastal salinity, oxygen and nutrient distributions

The formation of a subsurface anticyclonic eddy in the Peru-Chile Undercurrent (PCUC) in January and February 2013 is investigated using a multi-platform four-dimensional observational approach. Research vessel, multiple glider and mooring-based measurements were conducted in the Peruvian upwelling regime near 12°30'S. The dataset consists of more than 10000 glider profiles and repeated vessel-based hydrography and velocity transects. It allows a detailed description of the eddy formation and its impact on the near-coastal salinity, oxygen and nutrient distributions. In early January, a strong PCUC with maximum poleward velocities of ca. 0.25 m/s at 100 to 200 m depth was observed. Starting on January 20 a subsurface anticyclonic eddy developed in the PCUC downstream of a topographic bend, suggesting flow separation as the eddy formation mechanism. The eddy core waters exhibited oxygen concentrations less than 1mol/kg, an elevated nitrogen-deficit of ca. 17µmol/l and potential vorticity close to zero, which seemed to originate from the bottom boundary layer of the continental slope. The eddy-induced across-shelf velocities resulted in an elevated exchange of water masses between the upper continental slope and the open ocean. Small scale salinity and oxygen structures were formed by along-isopycnal stirring and indications of eddy-driven oxygen ventilation of the upper oxygen minimum zone were observed. It is concluded that mesoscale stirring of solutes and the offshore transport of eddy core properties could provide an important coastal open-ocean exchange mechanism with potentially large implications for nutrient budgets and biogeochemical cycling in the oxygen minimum zone off Peru.

Electron microprobe results of clay minerals from samples of the Frankenwald and the Thüringer Wald

Late Devonian (Frasnian) pillow basalts from the Frankenwald and Thüringer Wald within the Saxothuringian zone in Germany were found to contain abundant putative biogenic filaments, indicating that the volcanic rocks once harbored microbial life. The mineralized filaments are found in calcite-filled amygdules (former vesicles), where they started to form on internal surfaces of vesicles after seawater ingress. The filaments postdate an early fibrous carbonate cement but predate later equant calcite spar, revealing syngenetic formation. A biogenic origin of filaments is indicated by their size and morphology resembling modern microorganisms, their independence of crystal faces and cleavage plans, complex branching patterns, and internal segmentation. The filamentous microorganisms represent cryptoendoliths that lived in structural cavities of the basalt. They became preserved upon microbial clay authigenesis similar to the encrustation of modern prokaryotes in iron-rich environments. Filaments consist of clay minerals with the endmember composition berthierine-chamosite and illite-glauconite. Based on the discovery of fossilized filamentous microorganisms in Late Devonian pillow basalts of the Saxothurigian zone that are similar to filaments previously found in Middle Devonian pillow basalts of the Rhenohercynian zone, it is apparent that cryptoendolithic life was more widespread than previously recognized. Structural cavities within seafloor basalt may thus represent a common, perhaps universal niche for life in the oceanic crust.

Oxygen Utilization and Downward Carbon Flux in an Oxygen-Depleted Eddy in the Eastern Tropical North Atlantic

The occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40-100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, under water gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg-1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0-70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg-1 day-1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m-2 day-1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.