Fossil biomass preserved as graphitic carbon in a late paleoproterozoic banded iron formation metamorphosed at more than 550°C

Metamorphism is thought to destroy microfossils, partly through devolatilization and graphitization of biogenic organic matter. However, the extent to which there is a loss of molecular, elemental and isotope signatures from biomass during high-temperature metamorphism is not clearly established. We report on graphitic structures inside and coating apatite grains from the c. 1850 Ma Michigamme silicate banded iron formation from Michigan, metamorphosed above 550°C. Traces of N, S, O, H, Ca and Fe are preserved in this graphitic carbon and X-ray spectra show traces of aliphatic groups. Graphitic carbon has an expanded lattice around 3.6 Å, forms microscopic concentrically-layered and radiating polygonal flakes and has homogeneous δ13C values around −22‰, identical to bulk analyses. Graphitic carbon inside apatite is associated with nanometre-size ammoniated phyllosilicate. Precursors of these metamorphic minerals and graphitic carbon originated from ferruginous clayrich sediments with biomass. We conclude that graphite coatings and inclusions in apatite grains indicate fluid remobilization during amphibolite-facies metamorphism of precursor biomass. This new evidence fills in observational gaps of metamorphosed biomass into graphite and supports the existence of biosignatures in the highly metamorphosed iron formation from the Eoarchean Akilia Association, which dates from the beginning of the sedimentary rock record

A general perspective of the characterization and quantification of nanoparticles: Imaging, spectroscopic, and separation techniques

This article gives an overview of the different techniques used to identify, characterize, and quantify engineered nanoparticles (ENPs). The state-of-the-art of the field is summarized, and the different characterization techniques have been grouped according to the information they can provide. In addition, some selected applications are highlighted for each technique. The classification of the techniques has been carried out according to the main physical and chemical properties of the nanoparticles such as morphology, size, polydispersity characteristics, structural information, and elemental composition. Microscopy techniques including optical, electron and X-ray microscopy, and separation techniques with and without hyphenated detection systems are discussed. For each of these groups, a brief description of the techniques, specific features, and concepts, as well as several examples, are described.Junta de Andalucía FQM-5974CEI-Biotic Granada CEI2013- MP-1

Dynamics of CrO3–Fe2O3 catalysts during the high-temperature water-gas shift reaction: molecular structures and reactivity

A series of supported CrO3/Fe2O3 catalysts were investigated for the high-temperature water-gas shift (WGS) and reverse-WGS reactions and extensively characterized using in situ and operando IR, Raman, and XAS spectroscopy during the high-temperature WGS/RWGS reactions. The in situ spectroscopy examinations reveal that the initial oxidized catalysts contain surface dioxo (O═)2Cr6+O2 species and a bulk Fe2O3 phase containing some Cr3+ substituted into the iron oxide bulk lattice. Operando spectroscopy studies during the high-temperature WGS/RWGS reactions show that the catalyst transforms during the reaction. The crystalline Fe2O3 bulk phase becomes Fe3O4 ,and surface dioxo (O═)2Cr6+O2 species are reduced and mostly dissolve into the iron oxide bulk lattice. Consequently, the chromium–iron oxide catalyst surface is dominated by FeOx sites, but some minor reduced surface chromia sites are also retained. The Fe3–-xCrxO4 solid solution stabilizes the iron oxide phase from reducing to metallic Fe0 and imparts an enhanced surface area to the catalyst. Isotopic exchange studies with C16O2/H2 → C18O2/H2 isotopic switch directly show that the RWGS reaction proceeds via the redox mechanism and only O* sites from the surface region of the chromium–iron oxide catalysts are involved in the RWGS reaction. The number of redox O* sites was quantitatively determined with the isotope exchange measurements under appropriate WGS conditions and demonstrated that previous methods have undercounted the number of sites by nearly 1 order of magnitude. The TOF values suggest that only the redox O* sites affiliated with iron oxide are catalytic active sites for WGS/RWGS, though a carbonate oxygen exchange mechanism was demonstrated to exist, and that chromia is only a textural promoter that increases the number of catalytic active sites without any chemical promotion effect

Innovative methods in soil phosphorus research: A review

Phosphorus (P) is an indispensable element for all life on Earth and, during the past decade, concerns about the future of its global supply have stimulated much research on soil P and method development. This review provides an overview of advanced state-of-the-art methods currently used in soil P research. These involve bulk and spatially resolved spectroscopic and spectrometric P speciation methods (1 and 2D NMR, IR, Raman, Q-TOF MS/MS, high resolution-MS, NanoSIMS, XRF, XPS, (µ)XAS) as well as methods for assessing soil P reactions (sorption isotherms, quantum-chemical modeling, microbial biomass P, enzymes activity, DGT, 33P isotopic exchange, 18O isotope ratios). Required experimental set-ups and the potentials and limitations of individual methods present a guide for the selection of most suitable methods or combinations

Axial Ligation and Redox Changes at the Cobalt Ion in Cobalamin Bound to Corrinoid Iron-Sulfur Protein (CoFeSP) or in Solution Characterized by XAS and DFT

A cobalamin (Cbl) cofactor in corrinoid iron-sulfur protein (CoFeSP) is the primary methyl group donor and acceptor in biological carbon oxide conversion along the reductive acetyl-CoA pathway. Changes of the axial coordination of the cobalt ion within the corrin macrocycle upon redox transitions in aqua-, methyl-, and cyano-Cbl bound to CoFeSP or in solution were studied using X-ray absorption spectroscopy (XAS) at the Co K-edge in combination with density functional theory (DFT) calculations, supported by metal content and cobalt redox level quantification with further spectroscopic methods. Calculation of the highly variable pre-edge X-ray absorption features due to core-to-valence (ctv) electronic transitions, XANES shape analysis, and cobalt-ligand bond lengths determination from EXAFS has yielded models for the molecular and electronic structures of the cobalt sites. This suggested the absence of a ligand at cobalt in CoFeSP in α-position where the dimethylbenzimidazole (dmb) base of the cofactor is bound in Cbl in solution. As main species, (dmb)CoIII(OH2), (dmb)CoII(OH2), and (dmb)CoIII(CH3) sites for solution Cbl and CoIII(OH2), CoII(OH2), and CoIII(CH3) sites in CoFeSP-Cbl were identified. Our data support binding of a serine residue from the reductive-activator protein (RACo) of CoFeSP to the cobalt ion in the CoFeSP-RACo protein complex that stabilizes Co(II). The absence of an α-ligand at cobalt not only tunes the redox potential of the cobalamin cofactor into the physiological range, but is also important for CoFeSP reactivation

Impact of the Diamond Light Source on research in Earth and environmental sciences: current work and future perspectives.

Diamond Light Source Ltd celebrated its 10th anniversary as a company in December 2012 and has now accepted user experiments for over 5 years. This paper describes the current facilities available at Diamond and future developments that enhance its capacities with respect to the Earth and environmental sciences. A review of relevant research conducted at Diamond thus far is provided. This highlights how synchrotron-based studies have brought about important advances in our understanding of the fundamental parameters controlling highly complex mineral–fluid–microbe interface reactions in the natural environment. This new knowledge not only enhances our understanding of global biogeochemical processes, but also provides the opportunity for interventions to be designed for environmental remediation and beneficial use

Localization and chemical forms of cadmium in plant samples by combining analytical electron microscopy and X-ray spectromicroscopy

International audienceCadmium (Cd) is a metal of high toxicity for plants. Resolving its distribution and speciation in plants is essential for understanding the mechanisms involved in Cd tolerance, trafficking and accumulation. The model plant Arabidopsis thaliana was exposed to cadmium under controlled conditions. Elemental distributions in the roots and in the leaves were determined using scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX), and synchrotron-based micro X-ray fluorescence (μ-XRF), which offers a better sensitivity. The chemical form(s) of cadmium was investigated using Cd LIII-edge (3538 eV) micro X-ray absorption near edge structure (μ-XANES) spectroscopy. Plant μ-XANES spectra were fitted by linear combination of Cd reference spectra. Biological sample preparation and conditioning is a critical point because of possible artifacts. In this work we compared freeze-dried samples analyzed at ambient temperature and frozen hydrated samples analyzed at −170 °C. Our results suggest that in the roots Cd is localized in vascular bundles, and coordinated to S ligands. In the leaves, trichomes (epidermal hairs) represent the main compartment of Cd accumulation. In these specialized cells, μ-XANES results show that the majority of Cd is bound to O/N ligands likely provided by the cell wall, and a minor fraction could be bound to S-containing ligands. No significant difference in Cd speciation was observed between freeze-dried and frozen hydrated samples. This work illustrates the interest and the sensitivity of Cd LIII-edge XANES spectroscopy, which is applied here for the first time to plant samples. Combining μ-XRF and Cd LIII-edge μ-XANES spectroscopy offers promising tools to study Cd storage and trafficking mechanisms in plants and other biological samples

Chemical imaging analysis of the brain with X-ray methods

Cells employ various metal and metalloid ions to augment the structure and the function of proteins and to assist with vital biological processes. In the brain they mediate biochemical processes, and disrupted metabolism of metals may be a contributing factor in neurodegenerative disorders. In this tutorial review we will discuss the particular role of X-ray methods for elemental imaging analysis of accumulated metal species and metal-containing compounds in biological materials, in the context of post-mortem brain tissue. X-rays have the advantage that they have a short wavelength and can penetrate through a thick biological sample. Many of the X-ray microscopy techniques that provide the greatest sensitivity and specificity for trace metal concentrations in biological materials are emerging at synchrotron X-ray facilities. Here, the extremely high flux available across a wide range of soft and hard X-rays, combined with state-of-the-art focusing techniques and ultra-sensitive detectors, makes it viable to undertake direct imaging of a number of elements in brain tissue. The different methods for synchrotron imaging of metals in brain tissues at regional, cellular, and sub-cellular spatial resolution are discussed. Methods covered include X-ray fluorescence for elemental imaging, X-ray absorption spectrometry for speciation imaging, X-ray diffraction for structural imaging, phase contrast for enhanced contrast imaging and scanning transmission X-ray microscopy for spectromicroscopy. Two- and three-dimensional (confocal and tomographic) imaging methods are considered as well as the correlation of X-ray microscopy with other imaging tools

Metal species involved in long distance metal transport in plants

20 Pags.- 2 Tabls.- 1 Fig. © 2014 Álvarez-Fernández, Díaz-Benito, Abadía, López-Millán and Abadía. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) or licensor are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.The mechanisms plants use to transport metals from roots to shoots are not completely understood. It has long been proposed that organic molecules participate in metal translocation within the plant. However, until recently the identity of the complexes involved in the long-distance transport of metals could only be inferred by using indirect methods, such as analyzing separately the concentrations of metals and putative ligands and then using in silico chemical speciation software to predict metal species. Molecular biology approaches also have provided a breadth of information about putative metal ligands and metal complexes occurring in plant fluids. The new advances in analytical techniques based on mass spectrometry and the increased use of synchrotron X-ray spectroscopy have allowed for the identification of some metal-ligand species in plant fluids such as the xylem and phloem saps. Also, some proteins present in plant fluids can bind metals and a few studies have explored this possibility. This study reviews the analytical challenges researchers have to face to understand long-distance metal transport in plants as well as the recent advances in the identification of the ligand and metal-ligand complexes in plant fluids.This study was supported by the Spanish Ministry of Economy and Competitiveness (projects AGL2010-16515 and AGL2012-31988), and the Aragón Government (group A03). Pablo Díaz-Benito was supported by a MINECO-FPI grant.Peer reviewe

Investigation of the Effect of a Diamine-Based Friction Modifier on Micropitting and the Properties of Tribofilms in Rolling-Sliding Contacts

The effect of N-Tallow-1,3-DiaminoPropane (TDP) on friction, rolling wear and micropitting has been investigated with the ultimate objective of developing lubricants with no or minimal environmental impact. A Mini Traction Machine (MTM-SLIM) has been utilised in order to generate tribofilms and observe the effect of TDP on anti-wear tribofilm formation and friction. Micropitting was induced on the surface of specimens using a MicroPitting Rig (MPR). The X-ray Photoelectron Spectroscopy (XPS) surface analytical technique has been employed to investigate the effect of TDP on the chemical composition of the tribofilm while Atomic Force Microscopy (AFM) was used to generate high resolution topographical images of the tribofilms formed on the MTM discs. Experimental and analytical results showed that TDP delays the Zinc DialkylDithioPhosphate (ZDDP) anti-wear tribofilm formation. TDP in combination with ZDDP induces a thinner and smoother anti-wear tribofilm with a modified chemical structure composed of mixed Fe/Zn (poly)phosphates. The sulphide contribution to the tribofilm and oxygen-to-phosphorous atomic concentration ratio are greater in the bulk of the tribofilm derived from a combination of TDP and ZDDP compared to a tribofilm derived from ZDDP alone. Surface analysis showed that utilising TDP effectively mitigates micropitting wear in the test conditions used in this study. Reduction of micropitting, relevant to rolling bearing applications, can be attributed to the improved running-in procedure, reduced friction, formation of a smoother tribofilm and modification of the tribofilm composition induced by TDP