Laurent Remusat

NEUTRON-RICH CHROMIUM ISOTOPE ANOMALIES IN SUPERNOVA NANOPARTICLES

Neutron-rich isotopes with masses near that of iron are produced in Type Ia and II supernovae (SNeIa and SNeII). Traces of such nucleosynthesis are found in primitive meteorites in the form of variations in the isotopic abundance of ^(54)Cr, the most neutron-rich stable isotope of chromium. The hosts of these isotopic anomalies must be presolar grains that condensed in the outflows of SNe, offering the opportunity to study the nucleosynthesis of iron-peak nuclei in ways that complement spectroscopic observations and can inform models of stellar evolution. However, despite almost two decades of extensive search, the carrier of ^(54)Cr anomalies is still unknown, presumably because it is fine grained and is chemically labile. Here, we identify in the primitive meteorite Orgueil the carrier of ^(54)Cr anomalies as nanoparticles ( 3.6 × solar). Such large enrichments in ^(54)Cr can only be produced in SNe. The mineralogy of the grains supports condensation in the O/Ne-O/C zones of an SNII, although a Type Ia origin cannot be excluded. We suggest that planetary materials incorporated different amounts of these nanoparticles, possibly due to late injection by a nearby SN that also delivered ^(26)Al and ^(60)Fe to the solar system. This idea explains why the relative abundance of ^(54)Cr and other neutron-rich isotopes vary between planets and meteorites. We anticipate that future isotopic studies of the grains identified here will shed new light on the birth of the solar system and the conditions in SNe.

NanoSIMS Study of Organic Matter Associated with Soil Aggregates: Advantages, Limitations, and Combination with STXM

Direct observations of processes occurring at the mineral-organic interface are increasingly seen as relevant for the cycling of both natural soil organic matter and organic contaminants in soils and sediments. Advanced analytical tools with the capability to visualize and characterize organic matter at the submicrometer scale, such as Nano Secondary Ion Mass Spectrometry (NanoSIMS) and Scanning Transmission X-ray Microscopy (STXM) coupled to Near Edge X-ray Absorption Fine Structure Spectroscopy (NEXAFS), may be combined to locate and characterize mineral-associated organic matter. Taking advantage of samples collected from a decadal (15)N litter labeling experiment in a temperate forest, we demonstrate the potential of NanoSIMS to image intact soil particles and to detect spots of isotopic enrichment even at low levels of (15)N application. We show how microsites of isotopic enrichment detected by NanoSIMS can be speciated by STXM-NEXAFS performed on the same particle. Finally, by showing how (15)N enrichment at one microsite could be linked to the presence of microbial metabolites, we emphasize the potential of this combined imaging and spectroscopic approach to link microenvironment with geochemical process and/or location with ecological function.

Proto-Planetary Disk Chemistry Recorded by D-Rich Organic Radicals in Carbonaceous Chondrites

Insoluble organic matter (IOM) in primitive carbonaceous meteorites has preserved its chemical composition and isotopic heterogeneity since the solar system formed ∼4.567 billion years ago. We have identified the carrier moieties of isotopically anomalous hydrogen in IOM isolated from the Orgueil carbonaceous chondrite. Data from high spatial resolution, quantitative isotopic NanoSIMS mapping of Orgueil IOM combined with data from electron paramagnetic resonance spectroscopy reveals that organic radicals hold all the deuterium excess (relative to the bulk IOM) in distinct, micrometer-sized, D-rich hotspots. Taken together with previous work, the results indicate that an isotopic exchange reaction took place between pre-existing organic compounds characterized by low D/H ratios and D-rich gaseous molecules, such as H2D + or HD2 + . This exchange reaction most likely took place in the diffuse outer regions of the proto-planetary disk around the young Sun, offering a model that reconciles meteoritic and cometary isotopic compositions of organic molecules.

ACCRETION AND PRESERVATION OF D-RICH ORGANIC PARTICLES IN CARBONACEOUS CHONDRITES: EVIDENCE FOR IMPORTANT TRANSPORT IN THE EARLY SOLAR SYSTEM NEBULA

We have acquired NanoSIMS images of the matrices of CI, CM, and CR carbonaceous chondrites to study, in situ, the organic matter trapped during the formation of their parent bodies. D/H ratio images reveal the occurrence of D-rich hot spots, constituting isolated organic particles. Not all the organic particles are D-rich hot spots, indicating that at least two kinds of organic particles have been accreted in the parent bodies. Ratio profiles through D-rich hot spots indicate that no significant self-diffusion of deuterium occurs between the D-rich organic matter and the depleted hydrous minerals that are surrounding them. This is not the result of a physical shielding by any constituent of the chondrites. Ab initio calculations indicate that it cannot be explained by isotopic equilibrium. Then it appears that the organic matter that is extremely enriched in D does not exchange with the hydrous minerals, or this exchange is so slow that it is not significant over the 4.5 billion year history on the parent body. If we consider that the D-rich hot spots are the result of an exposure to intense irradiation, then it appears that carbonaceous chondrites accreted organic particles that have been brought to different regions of the solar nebula. This is likely the result of important radial and vertical transport in the early solar system.

A multi-scale approach to determine accurate elemental and isotopic ratios by nano-scale secondary ion mass spectrometry imaging

RATIONALE Nano-scale secondary ion mass spectrometry (NanoSIMS) is still hampered by a lack of appropriate calibration method for the quantification of elemental and isotopic ratios in heterogeneous materials such as soil samples. The potential of (13)C-(15)N-labeled density fractions of soil to calibrate the C/N, (13)C/(12)C and (15)N/(14)N ratios provided by NanoSIMS was evaluated. METHODS The spatial organization of soil particles found at the macro- and micro-scales were compared. The C/N, (13)C/(12)C and (15)N/(14)N ratios measured at the macroscopic scale from different density fractions using an elemental analyzer coupled to an isotope ratio mass spectrometer (EA/IRMS) were compared with the corresponding micro-scale NanoSIMS measurements. When the macro- and micro-scales patterns were similar, macroscopic scale measurements obtained by EA/IRMS and the corresponding NanoSIMS C/N and (15)N/(14)N ratios averaged per fraction were used to obtain correction equations. The correction method using the internal calibration procedure was compared with the traditional one using a single organic standard. RESULTS It was demonstrated that the correction method using an internal calibration procedure was applicable for NanoSIMS images acquired on more than 500 µm(2) per fraction and provided more accurate C/N and (15)N/(14)N ratios than the traditional correction method. CONCLUSIONS As long as the NanoSIMS sampling was representative of the macroscopic properties, the correction method using an internal calibration procedure allowed better quantification of the isotope tracers and characterization of the C/N ratios. This method not only produced qualitative images, but also accurate quantitative parameters from which ecological interpretations can be derived.

Micron-scale D/H heterogeneity in chondrite matrices: A signature of the pristine solar system water?

Abstract Organic matter and hydrous silicates are intimately mixed in the matrix of chondrites and in-situ determination of their individual D/H ratios is therefore challenging. Nevertheless, the D/H ratio of each pure component in this mixture should yield a comprehensible signature of the origin and evolution of water and organic matter in our solar system. We measured hydrogen isotope ratios of organic and hydrous silicates in the matrices of two carbonaceous chondrites (Orgueil CI1 and Renazzo CR2) and one unequilibrated ordinary chondrite (Semarkona, LL3.0). A novel protocol was adopted, involving NanoSIMS imaging of H isotopes of monoatomatic (H − ) and molecular (OH − ) secondary ions collected at the same location. This allowed the most enriched component with respect to D to be identified in the mixture. Using this protocol, we found that in carbonaceous chondrites the isotopically homogeneous hydrous silicates are mixed with D-rich organic matter. The opposite was observed in Semarkona. Hydrous silicates in Semarkona display highly heterogeneous D/H ratios, ranging from 150 to 1800 × 10 − 6 ( δ D SMOW = − 40 to 10 600‰). Organic matter in Semarkona does not show such large isotopic variations. This suggests limited isotopic exchange between the two phases during aqueous alteration. Our study greatly expands the range of water isotopic values measured so far in solar system objects. This D-rich water reservoir was sampled by the LL ordinary chondrite parent body and an estimate (≤9%) of its relative contribution to the D/H ratio of water in Oort cloud family comets is proposed.

Determination of the nitrogen abundance in organic materials by NanoSIMS quantitative imaging

We describe a procedure to determine precise and accurate elemental abundance by means of quantitative imaging using secondary ion mass spectrometry (on images covering ∼10 × 10 μm2) applied to natural Insoluble Organic Matter (IOM). Dynamic SIMS conditions are reached for a 16 keV Cs+ fluence of >2.0 × 1017 Cs+ cm−2 implanted at the surface of the IOM. Once the sample surface is saturated in cesium, steady-state implantation and sputtering yield are reached: constant secondary ion count rates are then observed. Two calibrations of the nitrogen abundance are presented. The nitrogen abundance is expressed either as [N] or N/C atomic ratio calibrated by means of 12C14N−/12C− or 12C14N−/12C2− ionic ratios respectively. The 12C14N−/12C− uncertainty is always larger than the uncertainty of 12C14N−/12C2−. At a smaller scale inside an image (∼1 × 1 μm2), a little larger than the primary beam size, processes induced by topographic irregularity of the IOM powder result in a variation of the 12C14N−,12C2− and 12C− count rates and increase the variability of the ionic ratios. The chemical contrast produced by a rough sample surface exposed to the Cs+ rastering is evaluated with a scratched epoxy resin for 12C14N−/12C− and 12C14N−/12C2− elemental ratios. Owing to similarities in emission parameters, the determination of the N/C ratio in rough organic surfaces is improved by using 12C 14N−/12C2− instead of 12C 14N−/12C−.

Fe biomineralization mirrors individual metabolic activity in a nitrate-dependent Fe(II)-oxidizer

Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is, however, thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had, however, never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II) oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate) encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with 13C-acetate, we provide evidence of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasmic encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a survival strategy in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern environmental samples.

Determination of the H isotopic composition of individual components in fine-scale mixtures of organic matter and phyllosilicates with the nanoscale secondary ion mass spectrometry.

When organic matter is mixed on a nanometer scale with clay minerals, the individual D/H ratios of the two H-bearing phases cannot be directly measured even with the nominal spatial resolution of nanoscale secondary ion mass spectrometry (NanoSIMS, 50-100 nm). To overcome this limitation, a new analytical protocol is proposed based on the deconvolution of the D(-)/H(-) and (16)OD(-)/(16)OH(-) ionic ratios measured by NanoSIMS. Indeed, since the yields of H(-) and (16)OH(-) are different for organics and clays, it should be theoretically possible to determine the mixing ratio of these two components in the area analyzed by the ion probe. Using organics with different D/H ratios, the interdependence of the D(-)/H(-) and (16)OD(-)/(16)OH(-) ionic ratios was determined in pure samples. Then using the H(-) and (16)OH(-) yields and the isotopic ratios measured on pure organic matter and clays, the expected D(-)/H(-) and (16)OD(-)/(16)OH(-) variations as a function of the mixing proportions were determined. These numerical predictions are consistent with measurements on laboratory prepared mixtures of D-rich organic matter and D-poor phyllosilicates, validating both the proposed experimental protocol and its use for meteorites. With an improvement of the precision of the ionic ratios by a factor of 10, it should possible to expend this protocol to samples having natural terrestrial D/H variations. Such an improvement could be attainable with the development of synthetic deuterated reference samples.

The deuterium/hydrogen distribution in chondritic organic matter attests to early ionizing irradiation

Primitive carbonaceous chondrites contain a large array of organic compounds dominated by insoluble organic matter (IOM). A striking feature of this IOM is the systematic enrichment in deuterium compared with the solar hydrogen reservoir. This enrichment has been taken as a sign of low-temperature ion-molecule or gas-grain reactions. However, the extent to which Solar System processes, especially ionizing radiation, can affect D/H ratios is largely unknown. Here, we report the effects of electron irradiation on the hydrogen isotopic composition of organic precursors containing different functional groups. From an initial terrestrial composition, overall D-enrichments and differential intramolecular fractionations comparable with those measured in the Orgueil meteorite were induced. Therefore, ionizing radiation can quantitatively explain the deuteration of organics in some carbonaceous chondrites. For these meteorites, the precursors of the IOM may have had the same isotopic composition as the main water reservoirs of the inner Solar System.