In situ atomic force microscopy measurements of biotite basal plane reactivity in the presence of oxalic acid

We have used a direct imaging technique, in situ atomic force microscopy (AFM), to observe the dissolution of the basal biotite surface by oxalic acid over a range of temperatures close to ambient conditions, using a specially designed AFM liquid cell and non-invasive intermittent contact mode of operation. From the 3-dimensional nanometre-resolution data sets, we observe a process characterised by the slow formation of shallow etch pits in the (0 0 1) surface and fast growth of etch pits from the resulting steps, which represent proxies for the {h k 0} surface. Measurements of dissolution rates as a function of temperature allow a determination of an apparent activation energy (E_a,app) for the process, via mass-loss calculations from image analysis. We obtain a value of E_a,app = 49 ± 2 kJ mol⁻¹, which is consistent with separate calculations based on planar area etch pit growth, and measurements of etch pit perimeters, indicating that this value of E_a,app is representative of {h k 0} surface dissolution. The measurement of etch pit perimeters also enables an estimation of apparent activation energy as a function of step density indicating substantially higher apparent activation energy, up to E_a,app = 140 kJ mol⁻¹, on extrapolation towards a pristine surface with no defects. We suggest that this higher value of E_a,app represents the slow formation of etch pits into the (0 0 1) surface.     

Estimation of surface latent heat fluxes from IRS-P4/MSMR satellite data

The brightness temperatures of the Microwave sensor MSMR (Multichannel Scanning Microwave Radiometer) launched in May 1999 onboard Indian Oceansat-1 IRS-P4 are used to develop a direct retrieval method for latent heat flux by multivariate regression technique. The MSMR measures the microwave radiances at 8 channels at frequencies of 6.6, 10.7, 18 and 21 GHz at both vertical and horizontal polarizations. It is found that the surface LHF (Latent Heat Flux) is sensitive to all the channels. The coefficients were derived using the National Centre for Environmental Prediction (NCEP) reanalysis data of three months: July, September, November of 1999. The NCEP daily analyzed latent heat fluxes and brightness temperatures observed by MSMR were used to derive the coefficients. Validity of the derived coefficients was checked within situ observations over the Indian Ocean and with NCEP analyzed LHF for global points. The LHF derived directly from the MSMR brightness temperature (Tb) yielded an accuracy of 35 watt/m². LHF was also computed by applying bulk formula using the geophysical parameters extracted from MSMR. In this case the errors were higher apparently due to the errors involved in derivation of the geophysical parameters.     

Postglacial topographic evolution of glaciated valleys: a stochastic landscape evolution model

The retreat of valley glaciers has a dramatic effect on the stability of glaciated valleys and exerts a prolonged influence on the subsequent fluvial sediment transport regime. We have studied the evolution of an idealized glaciated valley during the period following retreat of ice using a numerical model. The model incorporates a stochastic process to represent deep‐seated landsliding, non‐linear diffusion to represent shallow landsliding and an approximation of the Bagnold relation to represent fluvial sediment transport. It was calibrated using field data from several recent surveys within British Columbia, Canada. We present ensemble model results and compare them with results from a deterministic linear‐diffusion model to show that explicit representation of large landslides is necessary to reproduce the morphology and channel network structure of a typical postglacial valley. Our model predicts a rapid rate of fluvial sediment transport following deglaciation with a subsequent gradual decline, similar to that inferred for Holocene time. We also describe how changes in the model parameters affect the estimated magnitude and duration of the paraglacial sediment pulse. Copyright © 2005 John Wiley & Sons, Ltd.     

Geomorphologic and Palaeoenvironmental Development of Holocene Perched Coastal Dune Systems in Brittany, France

Two perched dune systems are investigated in the Baie d'Audierne (Finistère, Brittany, northwest France). A maximum age of 4545–4160 cal. yr bp for the onset of sand accretion is provided through radiocarbon (¹⁴C) analysis of an organic-rich basal palaeosol, corresponding closely to deceleration, but before stabilisation, of regional Holocene relative sea levels (RSLs). Molluscan analysis through the dune sand indicates an initial bare sand or sparsely vegetated surface, subsequently maturing and colonised by scrub vegetation, and finally returning to more open dune grassland conditions. These data suggest a three-stage Perched Dune Development Model (PDDM), which may be applicable to perched dunes on at least a regional scale: (1) initial sand sheet inundation as RSL rises; (2) stabilisation of RSL allowing dune to mature; and (3) sea-level stabilisation stimulates cliff formation, perching and progressive landward retreat of the dune shore. This study recognises that perched dunes hold greater potential for establishing chronologies for regional Holocene dune development than the more widely studied lowland dune systems, where evidence for early sand inundation may be obscured or lost by modest rises in sea level.     

Co-diagenesis of iron and phosphorus in hydrothermal sediments from the southern East Pacific Rise: Implications for the evaluation of paleoseawater phosphate concentrations

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ∼19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ∼12 m. Molar P/Fe ratios are then relatively constant to a depth of ∼35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.     

Geochemistry of Flooded Underground Mine Workings Influenced by Bacterial Sulfate Reduction

Unlike the majority of the water in the flooded mine complex of Butte Montana, which includes the highly acidic Berkeley pit lake, groundwater in the flooded West Camp underground mine workings has a circum-neutral pH and contains at least 8 μM aqueous sulfide. This article examines the geochemistry and stable isotope composition of this unusual H₂S-rich mine water, and also discusses problems related to the colorimetric analysis of sulfide in waters that contain FeS_(aq) cluster compounds. The West Camp mine pool is maintained at a constant elevation by continuous pumping, with discharge water that contains elevated Mn (90 μM), Fe (16 μM), and As (1.3 μM) but otherwise low metal concentrations. Dissolved inorganic carbon in the mine water is in chemical and isotopic equilibrium with rhodochrosite in the mineralized veins. The mine water is under-saturated with mackinawite and amorphous FeS, but is supersaturated with Cu- and Zn-sulfides. However, voltammetry studies show that much of the dissolved sulfide and ferrous iron are present as FeS_(aq) cluster molecules: as a result, the free concentration of the West Camp water is poorly constrained. Concentrations of dissolved sulfide determined by colorimetry were lower than gravimetric assays obtained by AgNO₃ addition, implying that the FeS_(aq) clusters are not completely extracted by the Methylene Blue reagent. In contrast, the clusters are quantitatively extracted as Ag₂S after addition of AgNO₃. Isotopic analysis of co-existing aqueous sulfide and sulfate confirms that the sulfide was produced by sulfate-reducing bacteria (SRB). The H₂S-rich mine water is not confined to the immediate vicinity of the extraction well, but is also present in flooded mine shafts up to 3 km away, and in samples bailed from mine shafts at depths up to 300 m below static water level. This illustrates that SRB are well established throughout the southwestern portion of the extensive (>15 km³) Butte flooded mine complex.     

Aliens like us?

Simon Conway Morris explains that as and when (and indeed if) we meet the extraterrestrials, they will look eerily like us.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.