A Mössbauer spectroscopic study of the iron redox transition in eastern Mediterranean sediments

Fe cycling at two sites in the Mediterranean Sea (southwest of Rhodes and in the North Aegean) has been studied, combining the pore water determination of nutrients, manganese, and iron, citrate-bicarbonate-dithionite (CDB) and total sediment extractions, X-ray diffraction, and ⁵⁷Fe Mössbauer spectroscopy (MBS). At the Rhodes site, double peaks in the CDB-extractable Mn and Fe profiles indicate non-steady-state diagenesis. The crystalline iron oxide hematite, identified at both sites by room temperature (RT) MBS, appears to contribute little to the overall Fe reduction. MBS at liquid helium temperature (LHT) revealed that the reactive sedimentary Fe oxide phase was nanophase goethite, not ferrihydrite as is usually assumed. The pore water data at both sites indicates that upon reductive dissolution of nanophase goethite, the upward diffusing dissolved Fe²⁺ is oxidized by Mn oxides, rather than by nitrate or oxygen. The observed oxidation of Fe²⁺ by Mn oxides may be more common than previously thought but not obvious in sediments where the nitrate penetration depth coincides with the Mn oxide peak. At the Rhodes site, the solid-phase Fe(II) increase occurred at a shallower depth than the accumulation of dissolved Fe²⁺ in the pore water. The deeper relict Mn oxide peak acts as an oxidation barrier for the upward diffusing dissolved Fe²⁺, thereby keeping the pore water Fe²⁺ at depth. At the North Aegean site, the solid-phase Fe(II) increase occurs at approximately the same depth as the increase in dissolved Fe²⁺ in the pore water. Overall, the use of RT and cryogenic MBS provided insight into the solid-phase Fe(II) gradient and allowed identification of the sedimentary Fe oxides: hematite, maghemite, and nanophase goethite.     

Vertical deformation partitioning across a collapsing large and hot orogen

Featuring 3 000-km-long large and hot orogen, the Mantiqueira Province provides a rare opportunity to study the process of gravitational collapse at mid to deep crustal levels. Distinct but contemporary (~500 Ma) post-collisional intrusions show structures and anisotropy of magnetic susceptibility (AMS) fabrics related to their emplacements, recording different flow patterns. In southern deep-seated intrusions, ellipsoidal-shaped roots with gabbroic-to-hybrid cores surrounded by granitic rocks show concentric patterns of AMS fabrics that cut across the NE-trending regional foliation. In contrast, northern intrusions, exposed as the upper sections of batholith-size bodies of coarse-grained granite emplaced at the shallow to mid-crust, show general NS-trending magnetic fabrics roughly parallel to strike of the orogen and the regional foliation of host rocks. These contrasting magnetic patterns from shallow to deeper crust suggest vertical magma migration from the overthickened orogenic core to be emplaced across its thinner stretched flanks during the gravitational collapse of the orogenic edifice.     

A late Ordovician (Hirnantian) karstic surface in a submarine channel,recording glacio‐eustatic sea‐level changes: Meifod,central Wales

The growth and decay of the end‐Ordovician Gondwanan glaciation is globally reflected by facies changes in sedimentary sequences, which record a major eustatic fall and subsequent rise in the Hirnantian Stage at the end of the Ordovician. However, there are different reported estimates of the magnitude and pattern of sea‐level change. Particularly good evidence for end‐Ordovician sea‐level change comes from a sequence at Meifod in central Wales, which has a karstified limestone unit within a channel incised into marine shelf sediments. Pre‐glacial (Rawtheyan) mudstones have a diverse fauna suggesting a mid‐to‐deep‐shelf water depth of c. 60 m. The channel, 20 m deep, was incised into these mudstones and partially filled with a mixture of fine sand and detrital carbonate. The taphonomy of bioclasts and intraclasts indicates that many had a long residence time on the sea floor or suffered diagenesis after shallow burial before being resedimented into the channel. The presence of carbonates on the Welsh shelf is atypical and they are interpreted as having accumulated as patches during a minor regression prior to the main glacio‐eustatic fall. Comparison of the carbon stable‐isotopic values of the bioclast material with the global isotopic record confirms that most of the material is of Rawtheyan age, but that some is Hirnantian. The resedimented carbonates lithified rapidly and formed a limestone, several metres thick, in the deepest parts of the channel. As sea‐level fell, this limestone was exposed and eroded into karstic domes and pillars with a relief of over 2 m. The overall, glacio‐eustatic, sea‐level fall is estimated to be in excess of 80 m. A succeeding sea‐level rise estimated to be 40–50 m is recorded in the laminated crust that mantles the karstic domes and pillars. The crust is formed of encrusting bryozoans, associated cystoids, crinoid holdfasts and clusters of the brachiopod Paromalomena, which is normally associated with mid‐shelf environments. Fine sands buried the karst topography and accumulated to fill the channel. In the sandstones at the base of the channel there is a Hirnantia fauna, while in the sandstones high in the channel‐sequence there is cross‐stratification characteristic of mid‐shoreface environments. This would indicate a fall of sea‐level of c. 30 m. The subsequent major transgression marking the end of the glaciation is not recorded at the Meifod locality, but nearby exposures of mudstones suggest a return to mid‐to‐deep‐shelf environments, similar to those that prevailed before the Hirnantian regression. The Meifod sequence provides strong evidence for the magnitude of the Hirnantian sea‐level changes and by implication confirm larger estimates for the size of the ice sheets. Smaller oscillations in relative sea‐level seen at Meifod may be local phenomena or may reflect eustatic changes that have not been widely reported elsewhere. Copyright © 2005 John Wiley & Sons, Ltd.     

Process regime change on a Silurian siliciclastic shelf: controlling influences on deposition of the Gray Sandstone Formation,Pembrokeshire, UK

Shallow marine deposits comprising the Silurian Gray Sandstone Formation (GSF) exhibit pronounced process regime changes through time. The formation was deposited on the southern shelf of the Lower Palaeozoic Welsh Basin (UK), and conformably overlies the Coralliferous Formation. The basal Lithofacies Assemblage A (of Sheinwoodian age) is dominated by a storm‐dominated process regime, comprising shoreface and offshore shelf facies associations. The overlying Lithofacies Assemblage B records a mixed process regime, with units being deposited under both storm‐ and tide‐influenced conditions. Tidal‐influence prevailed during deposition of the overlying Lithofacies Assemblage C, with proximal to distal facies variations across a significant tide‐influenced river delta being observed. A return to storm‐dominated shoreface conditions is seen in the succeeding Lithofacies Assemblage D. Lithofacies Assemblage E (Homerian age) records the return of a tide‐influenced river delta to the area, prior to the conformable transition into the overlying Old Red Sandstone (ORS) Red Cliff Formation (of Ludlow age). Northward thickening of the formation across southern Pembrokeshire into the Musselwick Fault indicates a tectonic control on sedimentation, the formation infilling accommodation space developed in an intra‐shelf half‐graben. Recurring changes in process regime from storm‐ to tide‐influenced sedimentation may be related to the onset and subsequent cessation of tidal resonance in sub‐basins across the shelf area which itself was probably controlled by episodic tectonism. It is proposed that the Coralliferous and Gray Sandstone formations comprise the newly erected Marloes Group. Copyright © 2009 John Wiley & Sons, Ltd.