Micro-scale investigation of carbonation process in partially serpentinized peridotites

The carbonation of ultramafic rocks is, theoretically, the most efficient reaction to trap CO2 irreversibly in the form of solid carbonates, as predicted by equilibrium thermodynamic calculations. However, the success of industrial or natural carbonation in large ultramafic aquifers or oceanic ultramafic exposures does not only rely on the thermodynamic conditions of chemical reactions, but also on their feedback effects on the reactive surface area and on the local porosity and permeability. In addition, side processes like serpentinization, redox reactions, abiotic catalytic effects, and biological activity, can be expected in such complex natural system. Their occurrence and implications on carbon speciation and carbon transfers during hydrothermal alteration of oceanic peridotites have not been explored yet and requires detailed study of natural and/or experimental carbonation zones. We have combined petrographic and electron microscopy with SIMS, Raman and FTIR microspectroscopy on partially serpentinized peridotites drilled during the IODP leg 304 (30 N, MAR) in order to characterize the mechanisms of peridotite carbonation at the fluid-mineral interface and identify the associated speciation of carbon (inorganic and organic carbon occurrences). We present first results on zones located close to talc-tremolite sheared veins in holes 1309B and D. Associations of carbonates, porous phyllosilicates and oxides are observed in close vicinity of relict olivines that underwent a previous stage of serpentinization. The olivine-carbonate interface is nanoporous which facilitates mass transfer between fluid and mineral. The phyllosilicate identified as saponite results from the metasomatic replacement, during the carbonation stage, of previously formed serpentine. These observations do not favour reaction-induced cracking but rather a transfer-controlled process in an open system. Among the submicrometric dark clusters widely-distributed in saponite and in serpentine, vibrational microspectroscopy reveals the presence of various types of organic compounds that tend to be located close to micrometric sulphides grains. Those results underline the microscale variability of carbon speciation within hydrothermally altered peridotites. The association of reduced carbon phases with the carbonation texture suggests that CO2 conversion may not be limited to solid carbonate formation in natural systems and that biological activity and/or abiotic CO2 reduction, possibly catalyzed by Ni-rich sulphides, can occur contemporaneously. This complex association of reactions has to be unravelled further to determine the respective contribution of abiotic versus biological processes and integrate them in carbon transfers modelling through the oceanic lithosphere

High-efficiency all-solution-processed light-emitting diodes based on anisotropic colloidal heterostructures with polar polymer injecting layers

Colloidal quantum dots (QDs) are emerging as true candidates for light-emitting diodes with ultrasaturated colors. Here, we combine CdSe/CdS dot-in-rod hetero-structures and polar/polyelectrolytic conjugated polymers to demonstrate the first example of fully solution-based quantum dot light-emitting diodes (QD-LEDs) incorporating all-organic injection/transport layers with high brightness, very limited roll-off and external quantum efficiency as high as 6.1%, which is 20 times higher than the record QD-LEDs with all-solution processed organic interlayers and exceeds by over 200% QD-LEDs embedding vacuum-deposited organic molecules

Malonate Crown Ethers as Building Blocks for Novel D-pi-A Chromophores

A series of new crown ethers, Incorporating a malonate ester functionality, have been synthesized and derivatized with pi-electron rich aldehydes; to give, conjugated, extended "push-pull" compounds. Their ability to bind Lewis acid-like metal cations, such as Mg2+ and Eu3+, has been characterized, and the relative stability constants are presented. When the metal cation is bound to the malonate moiety within the crown ether cavity, the D-pi-A character of the molecular structure is greatly enhanced

Cryptoendolithic colonization in the hydrating mantle along mid ocean ridges

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Mineralizations and transition metal mobility driven by organic carbon during low-temperature serpentinization

International audienceSerpentinization is known to provide substantial amounts of energy in the form of molecular hydrogen along with a suite of abiotic organic compounds of low molecular weight (mainly as short chain alkanes and carboxylic acids), all sustaining the development of microbial ecosystems in the mantle-derived crust. The latter have a cryptoendolithic life style and are responsible for (i) the local formation of biomass and of organic metabolic byproducts and (ii) the production of extracellular polymeric substances which organize the community in the form of a biofilm at the surface of the rock-forming minerals. In accordance, whatever their origin, organic compounds can be diverse and widespread in the shallow oceanic crust where they undergo hydrothermal degradation and remobilization through fluid circulations. Here we show that organic carbon is directly involved in low temperature serpentinization reactions (< 200 °C). Fine scale investigations of microbial niches hosted in serpentinites from the Mid-Atlantic ridge were performed using scanning and transmission electron microscopy along with scanning transmission X-ray microscopy. They suggest that organic coatings at mineral surfaces may influence the nature and structure of the serpentinization products as well as the mobility and speciation of transition metals as the reaction progresses. This likely constitutes an efficient yet poorly considered mechanism in active serpentinizing systems with possible implications for ore formation associated with the alteration of ophiolitic massifs and subsurface storage

Abiotic formation of condensed carbonaceous matter in the hydrating oceanic crust

Thermodynamic calculations suggest that condensed carbonaceous matter should be the dominant product of abiotic organic synthesis during serpentinization of the oceanic crust at Mid-Ocean Ridges. Here the authors report natural occurrences of such carbonaceous matter formed during low temperature alteration

A Class of Maximum-Period Nonlinear Congruential Generators Derived From the Rényi Chaotic Map

In this paper, a family of nonlinear congruential generators (NLCGs) based on the digitized Rényi map is considered for the definition of hardware-efficient pseudorandom number generators (PRNGs), and a theoretical framework for their study is presented. The authors investigate how the nonlinear structure of these systems eliminates some of the statistical regularities spoiling the randomness of sequences generated with linear techniques. In detail, in this paper, a necessary condition that the considered NLCGs must satisfy to have maximum period length is given, and a list of such maximum period PRNGs for period lengths up to 2 ^(31)-1 is provided. Referring to the NIST800-22 statistical test suite, two PRNG examples are presented and compared to well-known PRNGs based on linear recurrencies requiring a similar amount of resources for their implementation

Low temperature hydrothermal oil and associated biological precursors in serpentinites from Mid-Ocean Ridge

International audienceThe origin of light hydrocarbons discovered at serpentinite-hosted mid-ocean hydrothermal fields is generally attributed to the abiogenic reduction of carbon (di)oxide by molecular hydrogen released during the progressive hydration of mantle-derived peridotites. These serpentinization by-products represent a valuable source of carbon and energy and are known to support deep microbial ecosystems unrelated to photosynthesis. In addition, the pool of subsurface organic compounds could also include materials derived from the thermal degradation of biological material. We re-investigate the recently described relics of deep microbial ecosystems hosted in serpentinites of the Mid-Atlantic Ridge (4-6°N) in order to study the ageing and (hydro)thermal degradation of the preserved biomass. An integrated set of high resolution micro-imaging techniques (Scanning Electron Microscopy, High Resolution Transmission Electron Microscopy, Raman and Fourier Transform Infra-Red microspectroscopy, Confocal Laser Scanning Microscopy, and Scanning Transmission X-ray Microscopy at the carbon K-edge) has been applied to map the distribution of the different organic components at the micrometer scale and to characterize their speciation and structure. We show that biologically-derived material, containing aliphatic groups, along with carbonyl and amide functional groups, has experienced hydrothermal degradation and slight aromatization. In addition, aliphatic compounds up to C6-C10 with associated carboxylic functional groups wet the host bastite and the late serpentine veins crosscutting the rock. These compounds represent a light soluble organic fraction expelled after biomass degradation through oxidation and thermal cracking. The detected complex organic matter distribution recalls a typical petroleum system, where fossil organic matter of biological origin maturates, expelling the soluble fraction which then migrates from the source to the reservoir. Ecosystem-hosting serpentinites can thus be seen as source rocks generating a net transfer of hydrocarbons and/or fatty acids issued from oxidative processes and primary cracking reactions, then migrating upward through the serpentine vein network. This finally suggests that deep thermogenic organic compounds of biological origin can be a significant contributor to the organic carbon balance at and far below peridotite-hosted hydrothermal fields