Ferromanganese nodules and micro-hardgrounds associated with the Cadiz Contourite Channel (NE Atlantic): Palaeoenvironmental records of fluid venting and bottom currents

Ferromanganese nodule fields and hardgrounds have recently been discovered in the Cadiz Contourite Channel in the Gulf of Cadiz (850–1000 m). This channel is part of a large contourite depositional system generated by the Mediterranean Outflow Water. Ferromanganese deposits linked to contourites are interesting tools for palaeoenviromental studies and show an increasing economic interest as potential mineral resources for base and strategic metals. We present a complete characterisation of these deposits based on submarine photographs and geophysical, petrographic, mineralogical and geochemical data. The genesis and growth of ferromanganese deposits, strongly enriched in Fe vs. Mn (av. 39% vs. 6%) in this contourite depositional system result from the combination of hydrogenetic and diagenetic processes. The interaction of the Mediterranean Outflow Water with the continental margin has led to the formation of Late Pleistocene–Holocene ferromanganese mineral deposits, in parallel to the evolution of the contourite depositional system triggered by climatic and tectonic events. The diagenetic growth was fuelled by the anaerobic oxidation of thermogenic hydrocarbons (δ13CPDB=−20 to −37‰) and organic matter within the channel floor sediments, promoting the formation of Fe–Mn carbonate nodules. High 87Sr/86Sr isotopic values (up to 0.70993±0.00025) observed in the inner parts of nodules are related to the influence of radiogenic fluids fuelled by deep-seated fluid venting across the fault systems in the diapirs below the Cadiz Contourite Channel. Erosive action of the Mediterranean Outflow Water undercurrent could have exhumed the Fe–Mn carbonate nodules, especially in the glacial periods, when the lower core of the undercurrent was more active in the study area. The growth rate determined by 230Thexcess/232Th was 113±11 mm/Ma, supporting the hypothesis that the growth of the nodules records palaeoenvironmental changes during the last 70 ka. Ca-rich layers in the nodules could point to the interaction between the Mediterranean Outflow Water and the North Atlantic Deep Water during the Heinrich events. Siderite–rhodochrosite nodules exposed to the oxidising seabottom waters were replaced by Fe–Mn oxyhydroxides. Slow hydrogenetic growth of goethite from the seawaters is observed in the outermost parts of the exhumed nodules and hardgrounds, which show imprints of the Mediterranean Outflow Water with low 87Sr/86Sr isotopic values (down to 0.70693±0.00081). We propose a new genetic and evolutionary model for ferromanganese oxide nodules derived from ferromanganese carbonate nodules formed on continental margins above the carbonate compensation depth and dominated by hydrocarbon seepage structures and strong erosive action of bottom currents. We also compare and discuss the generation of ferromanganese deposits in the Cadiz Contourite Channel with that in other locations and suggest that our model can be applied to ferromanganiferous deposits in other contouritic systems affected by fluid venting.

Discovery of ferromanganese hydrocarbon-related nodules associated with the Meknes mud volcano (Western Moroccan margin)

A suite of ferromanganese nodules were sampled during the MVSEIS-2008 cruise aboard of the R/V Hespérides in the flanks of Meknes mud volcano (Moroccan margin, NE Central Atlantic). The nodules were collected at water depths between 750-850 m within a seabed area characterized by high acoustic backscatter values. Debris of cold water corals and hydrocarbon-derived authigenic carbonate crusts were sampled at same time. The nodules show tabular morphology, up to 20 cm in maximum diameter and 2 kg of weight, brown-reddish external color and they are internally composed by a concentric to complex arrangement of laminae. The results of X-ray diffraction analysis show that these ferromanganese nodules are essentially composed of goethite and lepidocrocite, being Mn-oxides, silicates (quartz and clay minerals) and carbonates (calcite, dolomite and siderite) accessory to occasional minerals. All the samples display micritic to micro-sparitic mosaic under the petrographic microscope which forms massive, laminated or dendritic-mottled textures. The nodules show a high abundance of Fe, minor Mn and low contents of trace metals and REEs. Mature hydrocarbons, as n-alkanes derived from marine bacterial activity, and phenanthrene have been detected in all the ferromanganese nodules analyzed. These nodules display analogous characteristics (textural, mineralogical and geochemical) to the nodules studied by González et al (2009) in the carbonate mud-mounds in the Gulf of Cadiz, offshore Iberian margin. In this way, the same preliminary genetic model proposed for these nodules might be applicable to those find in the Meknes mud volcano. Therefore, the anaerobic oxidation of hydrocarbon-rich fluids within the mud-breccia sediments in the flanks of Meknes mud volcano would induce the formation of early diagenetic Fe-(Mn) carbonate nodules. Thus, the nodules were later exhumed by the erosive action of sea bottom currents generating the replacement of ferromanganese carbonates by Fe-Mn oxy-hydroxides. Thus, the hydrocarbon-rich fluid venting from deep seated reservoirs and erosive action of bottom currents must have been essential actors, as mineralization controls, for ferromanganese nodules generation and evolution. These findings imply that this type of nodules must be considered as new product as derived from the anaerobic/aerobic oxidation of hydrocarbons in areas of active seepages.

Radiolarian-based paleotemperatures of ODP Site 177-1089 in the Atlantic Sector of the Southern Ocean

Two cores, Site 1089 (ODP Leg 177) and PS2821-1, recovered from the same location (40°56'S; 9°54'E) at the Subtropical Front (STF) in the Atlantic Sector of the Southern Ocean, provide a high-resolution climatic record, with an average temporal resolution of less than 600 yr. A multi-proxy approach was used to produce an age model for Core PS2821-1, and to correlate the two cores. Both cores document the last climatic cycle, from Marine Isotopic Stage 6 (MIS 6, ca. 160 kyr BP, ka) to present. Summer sea-surface temperatures (SSSTs) have been estimated, with a standard error of ca. +/-1.16°C, for the down core record by using Q-mode factor analysis (Imbrie and Kipp method). The paleotemperatures show a 7°C warming at Termination II (last interglacial, transition from MIS 6 to MIS 5). This transition from glacial to interglacial paleotemperatures (with maximum temperatures ca. 3°C warmer than present at the core location) occurs earlier than the corresponding shift in delta18O values for benthic foraminifera from the same core; this suggests a lead of Southern Ocean paleotemperature changes compared to the global ice-volume changes, as indicated by the benthic isotopic record. The climatic evolution of the record continues with a progressive temperature deterioration towards MIS 2. High-frequency, millennial-scale climatic instability has been documented for MIS 3 and part of MIS 4, with sudden temperature variations of almost the same magnitude as those observed at the transitions between glacial and interglacial times. These changes occur during the same time interval as the Dansgaard-Oeschger cycles recognized in the delta18Oice record of the GRIP and GISP ice cores from Greenland, and seem to be connected to rapid changes in the STF position in relation to the core location. Sudden cooling episodes ('Younger Dryas (YD)-type' and 'Antarctic Cold Reversal (ACR)-type' of events) have been recognized for both Termination I (ACR-I and YD-I events) and II (ACR-II and YD-II events), and imply that our core is located in an optimal position in order to record events triggered by phenomena occurring in both hemispheres. Spectral analysis of our SSST record displays strong analogies, particularly for high, sub-orbital frequencies, to equivalent records from Vostok (Antarctica) and from the Subtropical North Atlantic ocean. This implies that the climatic variability of widely separated areas (the Antarctic continent, the Subtropical North Atlantic, and the Subantarctic South Atlantic) can be strongly coupled and co-varying at millennial time scales (a few to 10-ka periods), and eventually induced by the same triggering mechanisms. Climatic variability has also been documented for supposedly warm and stable interglacial intervals (MIS 1 and 5), with several cold events which can be correlated to other Southern Ocean and North Atlantic sediment records.