40Ar-39Ar dating of high pressure metamorphic micas from the Gran Paradiso area (Western Alps): Evidence against the blocking temperature concept

The⁴⁰Ar-³⁹Ar method has been applied to high pressure (HP) white micas from the Gran Paradiso crystalline massif and from the overthrust Schistes Lustrés of its western slope. Preliminary petrographic and microanalytical investigation of the phengite micas showed that their celadonite-content decreases with time (from Si_3.65 to Si_3.05), and that less foliated samples are the most suitable for the metastable persistence of the high celadonite-content of the early HP stage during subsequent metamorphic evolution.Such samples were investigated together with one where mica is a pure retrogressive product. Two groups of plateau-ages have been found: (a) 60 to 75 Ma on HP phengites and early paragonites of unretrograded HP parageneses, thus dating the early HP metamorphic stage; (b) 38–40 Ma on HP phengites (most often in slightly retrograded HP parageneses) and on the purely retrogressive mica. For the HP phengites in (b), this age is considered to reflect the end of Ar readjustement during the later lowerP and/or higherT metamorphic stage, and not their crystallization.This disparity in plateau-ages for micas sampled within the same area shows that under the sameP-T conditions some systems were open while others remained closed. This can be closely related to the mineralogical behaviour: chemically active systems are isotopically active, whereby the reverse is not necessarily true. Thus, although temperature exceeded by far the usually assumed sealing-temperature of white micas, many systems have remained unaffected during the late Eocene event. Therefore, temperature cannot be the determining parameter for the opening of a system. Chemical reactivity, starting mineralogy and, primarily, pervasive deformation and the related fluid behaviour appear to be the effective controls.This implies that thermally activated diffusion processes (volume diffusion...) cannot be geologically significant. Consequently, the blocking temperature concept which rests on the opposite assumption now appears questionable. The fact that a mica does not necessarily behave as open above its blocking temperature necessitates at least a clear distinction between opening- and sealing-temperatures.     

The fusion crust of the Winchcombe meteorite: A preserved record of atmospheric entry processes

Fusion crusts form during the atmospheric entry heating of meteorites and preserve a record of the conditions that occurred during deceleration in the atmosphere. The fusion crust of the Winchcombe meteorite closely resembles that of other stony meteorites, and in particular CM2 chondrites, since it is dominated by olivine phenocrysts set in a glassy mesostasis with magnetite, and is highly vesicular. Dehydration cracks are unusually abundant in Winchcombe. Failure of this weak layer is an additional ablation mechanism to produce large numbers of particles during deceleration, consistent with the observation of pulses of plasma in videos of the Winchcombe fireball. Calving events might provide an observable phenomenon related to meteorites that are particularly susceptible to dehydration. Oscillatory zoning is observed within olivine phenocrysts in the fusion crust, in contrast to other meteorites, perhaps owing to temperature fluctuations resulting from calving events. Magnetite monolayers are found in the crust, and have also not been previously reported, and form discontinuous strata. These features grade into magnetite rims formed on the external surface of the crust and suggest the trapping of surface magnetite by collapse of melt. Magnetite monolayers may be a feature of meteorites that undergo significant degassing. Silicate warts with dendritic textures were observed and are suggested to be droplets ablated from another stone in the shower. They, therefore, represent the first evidence for intershower transfer of ablation materials and are consistent with the other evidence in the Winchcombe meteorite for unusually intense gas loss and ablation, despite its low entry velocity.     

The Holocene–Anthropocene transition in lakes of western Spitsbergen,Svalbard (Norwegian High Arctic): climate change and nitrogen deposition

Lake sediments from four small lakes on western Spitsbergen (Svalbard Archipelago, Norwegian High Arctic) preserve biostratigraphic and isotopic evidence for a complex suite of twentieth century environmental changes. At Lake Skardtjørna and Lake Tjørnskardet on Nordenskiöldkysten, there is a marked diatom floristic change coupled to increased diatom concentrations beginning around 1920. At Lake Istjørna and Lake Istjørnelva, 25 km southwest of Longyearbyen, both diatom total valve and chrysophyte stomatocyst concentrations have increased dramatically since the beginning of the 1900s. The early twentieth century changes are probably related to climate warming after the Little Ice Age. However, the most pronounced changes in diatom assemblages seem to have occurred in the last few decades. At the same time, nitrogen stable isotopes in sediment organic matter in two of the lakes became progressively depleted by ~2‰, which is consistent with diffuse atmospheric inputs from anthropogenic sources and attendant fertilization. These data suggest that climate change and nitrogen deposition may be acting together in driving these lakes towards new ecological states that are unique in the context of the Holocene.     

Valuing the non-CO2 climate impacts of aviation

The non-CO₂ climate impact of aviation (NO_x and contrails) is assessed and emissions weighting factors (EWFs) i.e., the factor by which aviation CO₂ emissions should be multiplied to get the CO₂-equivalent emissions for annual fleet average conditions are estimated. The EWFs are estimated using two economic metrics. One is based on the relative damage cost between non-CO₂ forcers and CO₂. The other is based on the cost-effective valuation between the non-CO₂ forcers and CO₂ given an upper ceiling on the global annual average surface temperature (set at 2?K above pre-industrial levels). We also estimate EWFs using three physical metrics, Global Warming Potential (GWP), Global Temperature change Potential (GTP) and Sustained GTP (SGTP) and compare our results with the economics based metrics. Given best estimates on the forcing contributions from CO₂, contrails and NO_x from aviation and by using a discount rate of 3%/year, the RDC based metric gives an EWF equal to 1.4 (slightly higher than EWFs based on GWP and SGTP using a 100?year time horizon). EWF using the cost-effective approach depends on the time that remains before stabilization occurs. It is roughly equal to unity until a few years before the temperature reaches its ceiling, and approximately 2 when stabilization has taken place. EWFs based on GTP resemble those based on CETO when the time left to when stabilization occurs is sufficiently large. Once stabilization has occurred CETO values resemble RDC based values. If aviation-induced cirrus clouds are included, uncertainties increase and the EWFs for GWP, SGTP and RDC based metrics end up in the range 1.3–2.9, while EWFs for GTP and CETO remain close to unity in the near term.     

Arsenite sequestration at the surface of nano-Fe(OH)2, ferrous-carbonate hydroxide, and green-rust after bioreduction of arsenic-sorbed lepidocrocite by Shewanella putrefaciens

X-ray Absorption Fine Structure (XAFS) spectroscopy was used in combination with high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), X-ray energy dispersive spectroscopy (XEDS), X-ray powder diffraction, and Mössbauer spectroscopy to obtain detailed information on arsenic and iron speciation in the products of anaerobic reduction of pure and As(V)- or As(III)-adsorbed lepidocrocite (γ-FeOOH) by Shewanella putrefaciens ATCC 12099. We found that this strain of S. putrefaciens is capable of using Fe(III) in lepidocrocite and As(V) in solution or adsorbed on lepidocrocite surfaces as electron acceptors. Bioreduction of lepidocrocite in the absence of arsenic resulted in the formation of hydroxycarbonate green rust 1 [Fe^II₄Fe^III₂(OH)₁₂CO₃: GR1(CO₃)], which completely converted into ferrous-carbonate hydroxide (Fe^II₂(OH)₂CO₃: FCH) over nine months. This study thus provides the first evidence of bacterial reduction of stoichiometric GR1(CO₃) into FCH. Bioreduction of As(III)-adsorbed lepidocrocite also led to the formation of GR1(CO₃) prior to formation of FCH, but the presence of As(III) slows down this transformation, leading to the co-occurrence of both phases after 22-month of aging. At the end of this experiment, As(III) was found to be adsorbed on the surfaces of GR1(CO₃) and FCH. After five months, bioreduction of As(V)-bearing lepidocrocite led directly to the formation of FCH in association with nanometer-sized particles of a minor As-rich Fe(OH)₂ phase, with no evidence for green rust formation. In this five-month experiment, As(V) was fully converted to As(III), which was dominantly sorbed at the surface of the Fe(OH)₂ nanoparticles as oligomers binding to the edges of Fe(OH)₆ octahedra at the edges of the octahedral layers of Fe(OH)₂. These multinuclear As(III) surface complexes are characterized by As-As pairs at a distance of 3.32 ± 0.02 Å and by As-Fe pairs at a distance of 3.50 ± 0.02 Å and represent a new type of As(III) surface complex. Chemical analyses show that the majority of As(III) produced in the experiments with As present is associated with iron-bearing hydroxycarbonate or hydroxide solids, reinforcing the idea that, at least under some circumstances, bacterial reduction can promote As(III) sequestration instead of mobilizing it into solution.     

NMR Measurements in Carbonate Rocks: Problems and an Approach to a Solution

Carbonate rocks are well known for their complex petrophysical behavior where, in contrast to siliciclastic rocks, different parameters, including porosity and permeability, usually are not directly related. This behavior is the result of thorough reorganization of porosity during diagenesis, and it turns prediction of reservoir quality of carbonate rocks into a challenge. The study presented here deals with the problem of utilizing NMR techniques in prediction of petrophysical properties in carbonates.We employ a visual porosity classification as a priori knowledge for better interpreting NMR data for prediction purposes. This allows for choice of suitable T₂ cutoff values to differentiate movable from bound fluids adapted for the specific carbonate rock, thus resulting in better interpretation of NMR data. The approach of using a genetic pore type classification for adapting the conventional method for T₂ cutoff determination, which originally was developed for siliciclastic rocks, is promising. Similarly, for permeability determination on the basis of NMR measurements, the classification of carbonate rocks based on porosity types also shows potential. The approach implemented here has the promise to provide a basis of standardized interpretation of NMR data from carbonate rocks.Acknowledgment We are grateful to Baker Hughes INTEQ, Celle, for permission to publish the results of this work. This study was part of I.S.s Masters Thesis at Hannover University that was carried out in collaboration with Baker Hughes INTEQ, Celle, Germany. We appreciate comments of an anonymous referee and PAGEOPH editor Brian J. Mitchell.