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 H_2D^+ or HD_2^+. 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

Chemical Mapping of Proterozoic Organic Matter at Sub-Micron Spatial Resolution

We have used a NanoSIMS ion microprobe to map sub-micron-scale distributions of carbon, nitrogen, sulfur, silicon, and oxygen in organic microfossils and laminae from the approximately 0.85 Ga Bitter Springs Formation of Australia. The data provide clues about the original chemistry of the microfossils, the silicification process, and biosignatures of specific microorganisms and microbial communities. Chemical maps of fossil unicells and filaments reveal distinct wall-and sheath-like structures enriched in C, N and S, consistent with their accepted biological origin. Surprisingly, organic laminae, previously considered to be amorphous, also exhibit filamentous and apparently compressed spheroidal structures defined by strong enrichments in C, N and S. By analogy to data from the well-preserved microfossils, these structures are interpreted as being of biological origin, most likely representing densely packed remnants of microbial mats. Because the preponderance of organic matter in Precambrian sediments is similarly "amorphous," our findings open a large body of generally neglected material to in situ structural, chemical, and isotopic study. Our results also offer new criteria for assessing biogenicity of problematic kerogenous materials and thus can be applied to assessments of poorly preserved or fragmentary organic residues in early Archean sediments and any that might occur in meteorites or other extraterrestrial samples

NanoSIMS opens a New Window for Deciphering Organic Matter in Terrestrial and Extraterrestrial Samples

Recognition of the earliest morphological or chemical evidence of terrestrial life has proved to be challenging, as organic matter in ancient rocks is commonly fragmentary and difficult to distinguish from abiotically-produced materials (Schopf, 1993; Van Zuilen et al., 2002; Altermann & Kazmierczak, 2003; Cady et al., 2003; Brasier et al., 2002, 2004, 2005; Hofmann, 2004; Skrzypczak et al., 2004, 2005). Yet, the ability to identify remnants of earliest life is critical to our understanding of the timing of life's origin on earth, the nature of earliest terrestrial life, and recognition of potential remnants of microbial life that might occur in extraterrestrial materials. The search for earliest life on Earth now extends to early Archean organic remains; these tend to be very poorly preserved and considerably more difficult to interpret than the delicately permineralized microfossils known from many Proterozoic deposits. Thus, recent efforts have been directed toward finding biosignatures that can help distinguish fragmentary remnants of ancient microbes from either pseudofossils or abiotic organic materials that may have formed hydrothermally or in extraterrestrial processes (House et al., 2000; Boyce et al., 2001; Kudryavtsev et al., 2001; Schopf, 2002; Schopf et al., 2002, 2005a,b; Cady et al., 2003; Garc a-Ruiz et al., 2003; Hofmann, 2004; Brasier et al., 2005; Rushdi and Simoneit, 2005; Skrzypczak et al., 2005). An exciting area of biosignature research involves the developing technology of NanoSIMS. NanoSIMS is secondary ion mass spectrometry (SIMS) for ultrafine feature, elemental and isotopic analysis. Its resolution approaches 0.05 micrometers for element mapping, which is 10-50 times finer than that attainable with conventional SIMS or electron microprobes. Consequently, NanoSIMS has the potential to reveal previously unknown, chemical and structural characteristics of organic matter preserved in geologic materials. Robert et al. (2005) were the first to combine NanoSIMS element maps with optical microscopic imagery in an effort to develop a new method for assessing biogenicity. They showed that the ability to simultaneously map the distribution of organic elements [such as carbon (C), nitrogen (N), and sulfur (S)] and compare those element distributions with optically recognizable, cellularly preserved fossils could provide significant new insights into the origin of organic materials in ancient sediments. This chapter details a recent NanoSIMS study which was designed to acquire new data relevant to establishing critical biosignatures (Oehler et al., 2006a-c). In this study, NanoSIMS was used to characterize element distributions of spheroidal and filamentous microfossils and associated organic laminae in chert from the approx. 0.85 billion year old (Ga) Bitter Springs Formation of Australia. Previous work established preservation of a diverse microbiota in the Bitter Springs Formation (Schopf, 1968; Schopf and Blacic, 1971), and there is no dispute within the scientific community regarding the biogenicity of any of the Bitter Springs structures evaluated in this new study. Thus, the NanoSIMS results described below provide new insight into - and can be used as a guide for assessing - the origin of less well understood organic materials that may occur in early Archean samples and in meteorites or other extraterrestrial samples

Mineralogy and petrology of comet 81P/wild 2 nucleus samples

The bulk of the comet 81P/Wild 2 (hereafter Wild 2) samples returned to Earth by the Stardust spacecraft appear to be weakly constructed mixtures of nanometer-scale grains, with occasional much larger (over 1 micrometer) ferromagnesian silicates, Fe-Ni sulfides, Fe-Ni metal, and accessory phases. The very wide range of olivine and low-Ca pyroxene compositions in comet Wild 2 requires a wide range of formation conditions, probably reflecting very different formation locations in the protoplanetary disk. The restricted compositional ranges of Fe-Ni sulfides, the wide range for silicates, and the absence of hydrous phases indicate that comet Wild 2 experienced little or no aqueous alteration. Less abundant Wild 2 materials include a refractory particle, whose presence appears to require radial transport in the early protoplanetary disk

Oxygen and magnesium mass-independent isotopic fractionation induced by chemical reactions in plasma

International audienceEnrichment or depletion ranging from −40 to +100% in the major isotopes 16 O and 24 Mg were observed experimentally in solids condensed from carbonaceous plasma composed of CO 2 /MgCl 2 /Pentanol or N 2 O/Pentanol for O and MgCl 2 /Pentanol for Mg. In NanoSims imaging, isotope effects appear as micrometer-size hotspots embedded in a carbonaceous matrix showing no isotope fractionation. For Mg, these hotspots are localized in carbonaceous grains, which show positive and negative isotopic effects so that the whole grain has a standard isotope composition. For O, no specific structure was observed at hotspot locations. These results suggest that MIF (mass-independent fractionation) effects can be induced by chemical reactions taking place in plasma. The close agreement between the slopes of the linear correlations observed between δ 25 Mg versus δ 26 Mg and between δ 17 O versus δ 18 O and the slopes calculated using the empirical MIF factor η discovered in ozone [M. H. Thiemens, J. E. Heidenreich, III. Science 219, 1073–1075; C. Janssen, J. Guenther, K. Mauersberger, D. Krankowsky. Phys. Chem. Chem. Phys . 3, 4718–4721] attests to the ubiquity of this process. Although the chemical reactants used in the present experiments cannot be directly transposed to the protosolar nebula, a similar MIF mechanism is proposed for oxygen isotopes: at high temperature, at the surface of grains, a mass-independent isotope exchange could have taken place between condensing oxides and oxygen atoms originated form the dissociation of CO or H 2 O gas

Trace element distribution between orthopyroxene and clinopyroxene in peridotites from the Gakkel Ridge: A SIMS and NanoSIMS study

Clinopyroxenes (cpx) in abyssal and ophiolitic peridotites are commonly analyzed for lithophile trace element abundances in order to estimate degrees of melting and porosity conditions during melt extraction, assuming that these data reflect near-solidus conditions. During cooling, however, cpxs always exsolve into parallel lamellae of low-Ca enstatite and high-Ca diopside. This may potentially lead to redistribution of the initial trace element budget. Since orthopyroxene (opx) cannot significantly host most incompatible trace elements, exsolution will lead to an enrichment in the cpx lamellae. In order to address a possibly exsolution-controlled partitioning between cpx and opx, we have obtained major and trace element mineral compositions on 14 plagioclase-free ocean floor mantle rocks. They cover the entire abyssal peridotite compositional spectrum from very fertile to highly depleted compositions. The mean volume proportion of opx lamellae in cpx porphyroclasts lies around 15% of the original cpx. For the light to middle rare earth elements, the enrichment in the measured cpx exsolution is exclusively controlled by these phase proportions. Relative to these highly incompatible trace elements, solely Ti and Yb partition significantly into opx. Lamellar interpyroxene partition coefficients, estimated from NanoSIMS analyses, are around three times as high as the ones for near-solidus bulk pyroxene. The equilibration temperatures for the exsolution lamella are slightly higher than 800°C. The bulk cpx can be reconstructed using the lamellar proportions and their relative partitioning. The implication of such a reconstruction is that the cpx rare earth element patterns shift almost in parallel to lower values. These shifts, however, do not affect mantle melting models proposed thus far for mid-ocean ridges. © Springer-Verlag 2005

Instantaneous healing of micro-fractures during coseismic slip: Evidence from microstructure and Ti in quartz geochemistry within an exhumed pseudotachylyte-bearing fault in tonalite

Exhumed faults within the tonalitic Adamello pluton (Southern Alps) were seismic at depth as indicated by the presence of pseudotachylytes (solidified friction-induced melts). During cooling of tonalite, early-formed joints were first exploited by localized ductile shear zones associated with deposition of quartz veins (at ~ 500 \ub0C), and later by pseudotachylyte-bearing cataclastic faults (at ~ 250\u2013300 \ub0C ambient temperature). Adjacent to pseudotachylytes, quartz of the host tonalite shows pervasive thin (1\u201310 \u3bcm wide) healed micro-fractures and ultra-fine (1\u20132 \u3bcm grain size) recrystallized aggregates along micro-shear zones. Under cathodoluminescence (CL) the healed micro-fractures have a darker gray shade than the host \u201cmagmatic\u201d quartz that reflects a change in Ti concentrations ([Ti]) as indicated by NanoSIMS measurements. [Ti] vary from 35\u201355 ppm in the CL-lighter host quartz to 10\u201313 ppm along the CL-darker healed micro-fractures. These [Ti] were inherited by the ultra-fine recrystallized aggregates that overprinted both the magmatic quartz and the healed micro-fractures during the high temperature transient related to frictional seismic slip. Based on Ti-in-quartz thermometry, we infer that micro-fracture healing occurred at higher temperatures than the ambient temperatures of faulting (250\u2013300 \ub0C at 0.2 GPa), for which [Ti] < 1 ppm would be expected. Micro-fracture healing can be ascribed to the stage of seismic slip of faults on the basis of the observation that: (i) they are absent in the host rock surrounding high-T quartz veins un-exploited by faults; and (ii) they locally occur at the tip of pseudotachylyte injection veins filling new fractures developed during the propagation of the earthquake rupture. The relatively high [Ti] of micro-fractures are therefore interpreted to reflect quartz healing by a fluid overheated during the initial stages of frictional seismic slip and escaping from fault surface through the damage zone. This suggests that, in the presence of fluids, thermal pressurization of the fault did not occur and did not prevent frictional melting. The small-scale microstructures and geochemistry of quartz in the wall of the studied paleo-seismic fault record a complex deformational history, referable to the short-lived (on the order of 104 s) thermal anomaly induced by frictional seismic slip, that includes both micro-fracture healing and recrystallization. This microstructural assemblage of the natural exhumed fault provides a key for understanding the mechanics of an earthquake source