Potential of EPR imaging to detect traces of primitive life in sedimentary rocks

In the prospect of the search for traces of primitive life on Earth and Mars, we investigated the possibility to detect and visualize the spatial distribution of minute amounts of organic matter in ancient rocks, in a non-destructive way, by Electron Paramagnetic Resonance Imaging (EPRI). We studied a series of non- or moderately metamorphosed siliceous rocks (cherts) of different ages ranging from 45 Ma to 3490 Ma and embedding fossile organic matter. In the case of the oldest cherts containing only mature insoluble organic matter (IOM), with IOM^• radicals characterized by a single Electron Paramagnetic Resonance (EPR) line, we could obtain three-dimensional images with sub-millimetric resolution of the organic matter distribution inside samples containing as low as 10¹⁴–10¹⁵ radicals per gram. In the case of younger cherts, containing less mature organic matter, and thus several types of organic radicals, we showed that selective imaging of each type of radical was possible provided that the EPR spectra did not overlap. Selective imaging of either the organic radicals or of the oxygen vacancy (E' centres) of the mineral matrix, which are ubiquitous in siliceous rocks, was possible, selecting either one or the other paramagnetic species with high power in-phase, 1st harmonic detection or with 90°-out-of-phase, 2nd harmonic detection of the EPR. The influence of ferromagnetic inclusions in the mineral matrix on the EPRI of the organic matter was also addressed. Image artifacts due to the ferromagnetic resonance signal of these inclusions could be easily removed by background substraction from the EPR spectra before image reconstruction. We thus showed that selective imaging by EPR of minute amounts of fossile organic matter in ancient rocks could be possible despite the magnetic complexity of such materials.     

Non-stationary future return levels for extreme rainfall over Extremadura (southwestern Iberian Peninsula)

Based on a previous study for temperature, a new method for the calculation of non-stationary return levels for extreme rainfall is described and applied to Extremadura, a region of southwestern Spain, using the peaks-over-threshold approach. Both all-days and rainy-days-only datasets were considered and the 20-year return levels expected in 2020 were estimated taking different trends into account: first, for all days, considering a time-dependent threshold and the trend in the scale parameter of the generalized Pareto distribution; and second, for rainy days only, considering how the mean, variance, and number of rainy days evolve. Generally, the changes in mean, variance and number of rainy days can explain the observed trends in extremes, and their extrapolation gives more robust estimations. The results point to a decrease of future return levels in 2020 for spring and winter, but an increase for autumn.     

Use of Markov Random Fields for automatic cloud/shadow detection on high resolution optical images

In this study, we propose an automatic detection algorithm for cloud/shadow on remote sensing optical images. It is based on physical properties of clouds and shadows, namely for a cloud and its associated shadow: both are connex objects of similar shape and area, and they are related by their relative locations. We show that these properties can be formalized using Markov Random Field (MRF) framework at two levels: one MRF over the pixel graph for connexity modelling, and one MRF over the graph of objects (clouds and shadows) for their relationship modelling. Then, we show that, practically, having performed an image pre-processing step (channel inter-calibration) specific to cloud detection, the local optimization of the proposed MRF models leads to a rather simple image processing algorithm involving only six parameters. Using a 39 image database, performance is shown and discussed, in particular in comparison with the Marked Point Process approach.     

Mean and variance evolutions of the hot and cold temperatures in Europe

In this paper, we examine the trends of temperature series in Europe, for the mean as well as for the variance in hot and cold seasons. To do so, we use as long and homogenous series as possible, provided by the European Climate Assessment and Dataset project for different locations in Europe, as well as the European ENSEMBLES project gridded dataset and the ERA40 reanalysis. We provide a definition of trends that we keep as intrinsic as possible and apply non-parametric statistical methods to analyse them. Obtained results show a clear link between trends in mean and variance of the whole series of hot or cold temperatures: in general, variance increases when the absolute value of temperature increases, i.e. with increasing summer temperature and decreasing winter temperature. This link is reinforced in locations where winter and summer climate has more variability. In very cold or very warm climates, the variability is lower and the link between the trends is weaker. We performed the same analysis on outputs of six climate models proposed by European teams for the 1961–2000 period (1950–2000 for one model), available through the PCMDI portal for the IPCC fourth assessment climate model simulations. The models generally perform poorly and have difficulties in capturing the relation between the two trends, especially in summer.     

Improving the Representation of the Nocturnal Near-Neutral Surface Layer in the Urban Environment with a Mesoscale Atmospheric Model

A new approach to improve the representation of surface processes in the Global Environmental Multiscale (GEM) atmospheric model associated with the exchanges between the urban canopy and the atmosphere is presented. Effects of the urban canopy on the evolution of surface-layer wind, temperature, moisture, and turbulence are directly parametrized in order to allow realistic interactions between the canopy elements (i.e., roofs, roads, and walls) and the atmosphere at GEM’s multiple vertical levels that are positioned inside the canopy. Surface energy budgets as implemented in the Town Energy Balance (TEB) scheme have been used to determine temperatures of the urban canopy elements for the proposed multilayer scheme. Performance of the multilayer scheme is compared against standard implementations of the TEB scheme for one nighttime intensive observation period of the Joint Urban 2003 experiment held in Oklahoma City, USA. Although the new approach is found to have a negligible impact on urban surface-layer wind profiles, it improves the prediction of near-neutral nocturnal profiles of potential temperature close to the surface. The urban heat island effect is simulated with a better accuracy by the multilayer approach. The horizontal temperature gradient across the central business district of the city along the direction of flow is also reasonably well captured by the proposed scheme.     

Hydrogen diffusion in spinel grain boundaries and consequences for chemical homogenization in hydrous peridotite

Hydrogen can be stored in the structure of nominally anhydrous minerals as point defects, and these impurities substantially modify many physical properties of Earth’s mantle minerals. However, mantle rocks are composed of mineral grains separated by grain boundaries and interphase grains boundaries. Therefore, as a potential hydrogen reservoir, grain boundaries should be given proper attention. Here, I report an experimental investigation into hydrogen diffusion through grain boundaries in polycrystalline aggregates. Sintering and diffusion experiments were performed using a gas-medium high-pressure vessel at under pressure of 300 MPa and over a temperature range of 900–1,250°C. The diffusion assembly consisted of a polycrystalline cylinder of aluminous spinel + olivine crystals with a talc cylinder as the main hydrogen source. A Ni capsule was used to buffer the oxygen fugacity at Ni–NiO. Experimental durations varied from 5 min to 5 h. The presence of hydrogen in the crystals was measured by Fourier-transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the characteristic distance. The absence or presence of hydrogen recorded by the ‘hydrogen sensor’ olivines embedded in the aggregate allows the estimation of bounds on this characteristic distance. Results presented here suggest that hydrogen effective diffusion coefficients are only one order of magnitude faster (~10⁻⁹ m²s⁻¹ at 1,000°C) than in an olivine single crystal along the [100] axis. Resulting diffusion coefficients for hydrogen in grain boundary are four orders of magnitude faster than in a single crystal, but this diffusivity is not fast enough to affect hydrogen mobility in mantle rocks with grain sizes greater than ~1 mm. Thus, very limited chemical homogenization would occur using grain boundaries diffusion in mantle hydrous peridotite for incompatible and volatile element, such as hydrogen.     

Non‐uniform splitting of a single mantle plume by double cratonic roots: Insight into the origin of the central and southern East African Rift System

Using numerical thermo‐mechanical experiments we analyse the role of an active mantle plume and pre‐existing lithospheric thickness differences in the structural development of the central and southern East African Rift system. The plume‐lithosphere interaction model setup captures the essential features of the studied area: two cratonic bodies embedded into surrounding lithosphere of normal thickness. The results of the numerical experiments suggest that localization of rift branches in the crust is mainly defined by the initial position of the mantle plume relative to the cratons. We demonstrate that development of the Eastern branch, the Western branch and the Malawi rift can be the result of non‐uniform splitting of the Kenyan plume, which has been rising underneath the southern part of the Tanzanian craton. Major features associated with Cenozoic rifting can thus be reproduced in a relatively simple model of the interaction between a single mantle plume and pre‐stressed continental lithosphere with double cratonic roots.     

Heat flow estimates offshore Haiti in the Caribbean plate

Heat‐flow in the Caribbean is poorly known and generally low in the major basins and the Greater Antilles arc, but with some high values in active zones, like in the Cayman trough or in the Lesser Antilles Arc. Here we present new heat‐flow data for offshore Haiti, which is part of the Greater Antilles arc. We obtain new heat‐flow estimates from in situ measurements and Bottom Simulating Reflector (BSR). Both methods suggest a regionally low heat‐flow, respectively 46 ± 7 and 44 ± 12 mW/m², with locally high values exceeding 80 mW/m². The high heat‐flow values are generally located near faults, and could be related to fluid circulations. Our study confirms a low heat‐flow pattern at the scale of the Caribbean but points out the existence of local‐scale variability with high heat‐flow along the northern faults of the Caribbean region.     

Urban hydrologic trend analysis based on rainfall and runoff data analysis and conceptual model calibration

Urban stormwater is a major cause of urban flooding and natural water pollution. It is therefore important to assess any hydrologic trends in urban catchments for stormwater management and planning. This study addresses urban hydrological trend analysis by examining trends in variables that characterize hydrological processes. The original and modified Mann‐Kendall methods are applied to trend detection in two French catchments, that is, Chassieu and La Lechere, based on approximately 1 decade of data from local monitoring programs. In both catchments, no trend is found in the major hydrological process driver (i.e., rainfall variables), whereas increasing trends are detected in runoff flow rates. As a consequence, the runoff coefficients tend to increase during the study period, probably due to growing imperviousness with the local urbanization process. In addition, conceptual urban rainfall‐runoff model parameters, which are identified via model calibration with an event based approach, are examined. Trend detection results indicate that there is no trend in the time of concentration in Chassieu, whereas a decreasing trend is present in La Lechere, which, however, needs to be validated with additional data. Sensitivity analysis indicates that the original Mann‐Kendall method is not sensitive to a few noisy values in the data series.     

Mechanisms of hydrogen incorporation and diffusion in iron-bearing olivine

The incorporation and diffusion of hydrogen in San Carlos olivine (Fo₉₀) single crystals were studied by performing experiments under hydrothermal conditions. The experiments were carried out either at 1.5 GPa, 1,000°C for 1.5 h in a piston cylinder apparatus or at 0.2 GPa, 900°C for 1 or 20 h in a cold-seal vessel. The oxygen fugacity was buffered using Ni–NiO, and the silica activity was buffered by adding San Carlos orthopyroxene powders. Polarized Fourier transform infrared (FTIR) spectroscopy was utilized to quantify the hydroxyl distributions in the samples after the experiments. The resulting infrared spectra reproduce the features of FTIR spectra that are observed in olivine from common mantle peridotite xenoliths. The hydrogen concentration at the edges of the hydrogenated olivine crystals corresponds to concentration levels calculated from published water solubility laws. Hydrogen diffusivities were determined for the three crystallographic axes from profiles of water content as a function of position. The chemical diffusion coefficients are comparable to those previously reported for natural iron-bearing olivine. At high temperature, hydrogenation is dominated by coupled diffusion of protons and octahedrally coordinated metal vacancies where the vacancy diffusion rate limits the process. From the experimental data, we determined the following diffusion laws (diffusivity in m² s⁻¹, activation energies in kJ mol⁻¹): for diffusion along [100] and [010]; for diffusion along [001]. These diffusion rates are fast enough to modify significantly water contents within olivine grains in xenoliths ascending from the mantle.