High‐Precision,High‐Accuracy Oxygen Isotope Measurements of Zircon Reference Materials with the SHRIMP‐SI

Analytical protocols for SHRIMP‐SI oxygen isotope analysis (δ¹⁸O) of a suite of zircon reference materials (RMs) are presented. Data reduction involved a robust estimate of uncertainties associated with the individual spot as well as for groups where the spot data are combined. The repeatability of δ¹⁸O measurements is dependent on both the analytical conditions and the choice of the primary reference material. Under optimised conditions, repeatability was often better than 0.4‰ (2s) allowing sample uncertainties to be obtained to better than 0.2‰ (at 95% confidence limit). Single spot uncertainty combined the within‐spot precision with the scatter associated with repeated measurements of the primary zircon reference material during a measurement session. The uncertainty for individual spots measured under optimised conditions was between 0.3 and 0.4‰ (at 95% confidence). The analytical protocols described were used to assess a variety of zircon RMs that have been used for geochronology and for which laser fluorination oxygen isotope data are available (Temora 2, FC1, R33, QGNG and Ple?ovice), as well as zircons that have been used as RMs for trace element or other types of determination (Mud Tank, Monastery, 91500, AS57, AS3, KIM‐5, OG1, SL13, CZ3 and several other Sri Lankan zircons). Repeated analyses over nine sessions and seven different mounts show agreement within analytical uncertainty for Temora 2, FC1, R33, QGNG, Ple?ovice and 91500, when normalised to Mud Tank. For existing ion microprobe mounts with these materials, an appropriate δ¹⁸O can be determined. However, care should be taken when using zircons from the Duluth Complex (i.e., FC1, AS57 and AS3) as reference materials as our data indicated an excess scatter on δ¹⁸O values associated with low‐U zircon grains.     

Potential of legacy 2D seismic data for deep targeting and structural imaging at the Neves–Corvo massive sulphide-bearing deposit,Portugal

Seismic methods are becoming an established choice for deep mineral exploration after being extensively tested and employed for the past two decades. To investigate whether the early European mineral-exploration datasets had potential for seismic imaging that was overlooked, we recovered a low-fold legacy seismic dataset from the Neves–Corvo mine site in the Iberian Pyrite Belt in southern Portugal. This dataset comprises six 4–6 km long profiles acquired in 1996 for deep targeting. Using today's industry-scale processing algorithms, the world-class, ca. 150 Mt, Lombador massive sulphide and other smaller deposits were better imaged. Additionally, we also reveal a number of shallow but steeply dipping reflections that were absent in the original processing results. This study highlights that legacy seismic data are valuable and should be revisited regularly to take advantage of new processing algorithms and the experiences gained from processing such data in hard-rock environments elsewhere. Remembering that an initial processing job in hard rock should always aim to first obtain an overall image of the subsurface and make reflections visible, and then subsequent goals of the workflow could be set to, for example understanding relative amplitude ratios. The imaging of the known mineralization implies that this survey could likely have been among one of the pioneer studies in the world that demonstrated the capability of directly imaging massive sulphide deposits using the seismic method.     

Greigite: a true intermediate on the polysulfide pathway to pyrite

The formation of pyrite (FeS₂) from iron monosulfide precursors in anoxic sediments has been suggested to proceed via mackinawite (FeS) and greigite (Fe₃S₄). Despite decades of research, the mechanisms of pyrite formation are not sufficiently understood because solid and dissolved intermediates are oxygen-sensitive and poorly crystalline and therefore notoriously difficult to characterize and quantify.     

Palaeontology and taphonomy of Late Quaternary fossil assemblages at Somersham,Cambridgeshire, England,and the problem of reworking

Assemblages of foraminifers, ostracods and molluscs from temperate Ipswichian Stage (last temperate stage) sediments and overlying cold Devensian Stage (last cold stage) sediments at Somersham in the southern Fenland of Cambridgeshire have been analysed. The Ipswichian sediments contain faunas consistent with temperate brackish water conditions under tidal influence. The Devensian assemblages were recovered from a series of sands and gravels laterally accreting in a channel cutting into Ipswichian sediments. In contrast to the Ipswichian faunas, the faunas of particular Devensian samples show a complex mixture of temperate freshwater, brackish and marine taxa. The molluscs are mainly freshwater, with few land snails; they occur together with foraminifers and ostracods. Freshwater, brackish water and marine ostracods are present with foraminifers. A sample of Devensian fine laminated sediment in the channel was analysed for pollen; only abundant pre-Quaternary spores were present, with abundant foraminifers in the same sample. The taphonomy of the assemblages and the difficulties of their interpretation in environmental terms are discussed. The importance of taphonomy in assessing environments, climate, range of taxa and dating is stressed.     

Bioavailable iron in the Southern Ocean: the significance of the iceberg conveyor belt

Productivity in the Southern Oceans is iron-limited, and the supply of iron dissolved from aeolian dust is believed to be the main source from outside the marine reservoir. Glacial sediment sources of iron have rarely been considered, as the iron has been assumed to be inert and non-bioavailable. This study demonstrates the presence of potentially bioavailable Fe as ferrihydrite and goethite in nanoparticulate clusters, in sediments collected from icebergs in the Southern Ocean and glaciers on the Antarctic landmass. Nanoparticles in ice can be transported by icebergs away from coastal regions in the Southern Ocean, enabling melting to release bioavailable Fe to the open ocean. The abundance of nanoparticulate iron has been measured by an ascorbate extraction. This data indicates that the fluxes of bioavailable iron supplied to the Southern Ocean from aeolian dust (0.01–0.13 Tg yr^-1) and icebergs (0.06–0.12 Tg yr^-1) are comparable. Increases in iceberg production thus have the capacity to increase productivity and this newly identified negative feedback may help to mitigate fossil fuel emissions.     

Spinning with the dinosaurs: the fossil record of spiders

When most people hear the word 'fossil' they tend to conjure up images of giant dinosaurs such as Tyrannosaurus rex or shelled marine invertebrates. Prior to the Hollywood blockbuster movie Jurassic Park , which was based on recreating dinosaurs through extracting their DNA from fossil mosquitoes preserved in amber, few non-palaeontologists would entertain the notion that small, soft-bodied organisms such as insects occur in the fossil record. However, insects and spiders are common as fossils in amber, where they are often preserved with life-like fidelity, and they also occur to a lesser degree in carbonate rocks.     

Quantification of initial steps of nucleation and growth of silica nanoparticles: An in-situ SAXS and DLS study

The initial steps of silica polymerization and silica nanoparticle formation have been studied in-situ and in real-time. The experiments were carried out in near neutral pH (7–8) solutions with initial silica concentrations of 640 and 1600 ppm ([SiO₂]) and ionic strengths (IS) of 0.02, 0.05, 0.11 and 0.22 M. The polymerization reactions were induced by neutralizing a high pH silica solution (from pH 12 to 7) and monitored by the time-dependent depletion in monosilicic acid concentration over time. The accompanied nucleation and growth of silica nanoparticles (i.e., change in particle size over time) was followed in-situ using time-resolved synchrotron-based Small Angle X-ray Scattering (SAXS) and conventional Dynamic Light Scattering (DLS) combined with scanning and (cryo)-transmission electron microscopy (SEM/cryo-TEM).The critical nucleus diameter was quantified (1.4–2 nm) and results from SAXS and DLS showed that over 3 h the particle diameter increased to a final size of 8 nm. SEM and TEM photomicrographs verified the SAXS and DLS data and confirmed the spherical and hydrous structure of the forming silica nanoparticles. Furthermore, fractal analysis (i.e., fractal dimension, D_m  2.2) indicated that the formed particles consisted of open, polymeric, low-density structures.For the nucleation and growth of silica nanoparticles a 3-stage growth process is proposed: (1) homogeneous and instantaneous nucleation of silica nanoparticles, (2) 3-D, surface-controlled particle growth following 1st order reaction kinetics and (3) Ostwald ripening and particle aggregation.     

Subsidence and flexure along the Pratt-Welker seamount chain

Chemical and age data led Turner, Jarrard and Forbes to conclude that the origin of the Pratt-Welker seamount chain in the Gulf of Alaska cannot be attributed to a single cause. They argued instead that some seamounts in the chain formed over a hotspot, away from a ridge, while others formed near a ridge. They also noted that the latter group of guyots were generally deeper than the former and they used this observation to predict the origin of the unsampled seamounts in the chain. A second geophysical test of the origin hypothesis is to examine the degree of isostatic compensation of the guyots; seamounts formed near a ridge should be in a state of local isostatic compensation, while seamounts formed away from a ridge should be regionally compensated. This test has been carried out using GEOS 3 and SEASAT altimeter data. The effective flexural rigidity of the lithosphere below all seamounts is found to be less than about 10²⁰ Nm, such that the isostatic state is nearly local, rather than regional. This may be a consequence of all the seamounts having formed on an initially weak lithosphere, of stress relaxation subsequant to their formation away from the ridge, or both. If the seamounts from Giacomini to Durgin formed away from the ridge then these results point to an effective flexural rigidity at the time of loading of about 3 × 10²¹ Nm and to a stress-relaxation time of about 10⁶ years. These values are for an ocean lithosphere that was about 20–22 my old when loaded. Corresponding values for 60 my old lithosphere in the southern Pacific were previously found to be about 3 × 10²² Nm and 5 × 10⁶ years. This comparison suggests that both the initial elastic response and the rate of stress relaxation are functions of the age of the lithosphere. The subsidence of guyots is due to numerous factors including thermal contraction of the seafloor, sediment loading, the flexure of the lithosphere prior to its subduction along the Aleutian Trench and, in view of the above short stress relaxation time, stress relaxation. A principal uncertainty in evaluating the subsidence that has occurred subsequent to the seamount having been eroded to sealevel is the erosion time interval. The comparison of the predicted subsidence with observed depths points to an erosion time constant of the order of 5 my and which is a function of seamount size. The conclusions from the flexure and subsidence analysis as to where the various seamounts formed are in agreement with those of Turner et al. Giacomini, Quinn, Surveyor, Pratt and Durgin formed away from a ridge and are consistent with a fixed hotspot and uniform spreading rate model. The geophysical information for Denson, Davidson and Hodgkins is consistent with the hypothesis that these guyots formed near or on a ridge. The case for Welker seamount is ambiguous, and this guyot may have formed over a second hotspot, located at an intermediate distance between the first and the ridge. The geophysical evidence for Bowie seamount is also ambiguous. Possibly it has a similar source to Welker, suggesting that there may actually be three different origin mechanisms that led to the chain.     

Elsterian‐Holsteinian deposits at Kås Hoved,northern Denmark: sediments,foraminifera, ostracods,and stable isotopes

The coastal cliff section at Kås Hoved in northern Denmark represents one of the largest exposures of marine interglacial deposits in Europe. High‐resolution analyses of sediments, foraminifera, ostracods, and stable isotopes (oxygen and carbon) in glacial‐interglacial marine sediments from this section, as well as from two adjacent boreholes, are the basis for an interpretation of marine environmental and climatic change through the Late Elsterian‐Holsteinian glacial‐interglacial cycle. The overlying glacial deposits show two ice advances during the Saalian and Weichselian glaciations. The assemblages in the initial glacier‐proximal part of the marine Late Elsterian succession reveal fluctuations in the inflow of sediment‐loaded meltwater to the area. This is followed by faunal indication of glacier‐distal, open marine conditions, coinciding with a gradual climatic change from arctic to subarctic environments. Continuous marine sedimentation during the glacial‐interglacial transition is presumably a result of a large‐scale isostatic subsidence caused by the preceding extended Elsterian glaciation. The similarity of the climatic signature of the interglacial Holsteinian and Holocene assemblages in this region indicates that the Atlantic Ocean circulation was similar during these two interglacials, whereas Eemian interglacial assemblages indicate a comparatively high water temperature associated with an enhanced North Atlantic Current. The foraminiferal zones are correlated with other Elsterian‐Holsteinian sites in Denmark, as well as those in the type area for the Holsteinian interglacial in northern Germany and the southern North Sea. Correlation of the NW European Holsteinian succession with the marine isotope stages MIS 7, 9 or 11 is still unresolved.     

What controls selenium release during shale weathering?

This study demonstrates that only a combination of a chromous chloride reduction with dual sequential extraction schemes can clearly separate the proportions of Se present in the sulphide versus the organic pools in shales. The data reveals that even small amounts of pyrite outcompete the organic matter for the available Se and pyrite oxidation will control the release of selenium during shale weathering.