Soft-Tissue, Rare Earth Element, and Molecular Analyses of Dreadnoughtus schrani, an Exceptionally Complete Titanosaur from Argentina.

Evidence that organic material preserves in deep time (>1 Ma) has been reported using a wide variety of analytical techniques. However, the comprehensive geochemical data that could aid in building robust hypotheses for how soft-tissues persist over millions of years are lacking from most paleomolecular reports. Here, we analyze the molecular preservation and taphonomic history of the Dreadnougtus schrani holotype (MPM-PV 1156) at both macroscopic and microscopic levels. We review the stratigraphy, depositional setting, and physical taphonomy of the D. schrani skeletal assemblage, and extensively characterize the preservation and taphonomic history of the humerus at a micro-scale via: (1) histological analysis (structural integrity) and X-ray diffraction (exogenous mineral content); (2) laser ablation-inductively coupled plasma mass spectrometry (analyses of rare earth element content throughout cortex); (3) demineralization and optical microscopy (soft-tissue microstructures); (4) in situ and in-solution immunological assays (presence of endogenous protein). Our data show the D. schrani holotype preserves soft-tissue microstructures and remnants of endogenous bone protein. Further, it was exposed to LREE-enriched groundwaters and weakly-oxidizing conditions after burial, but experienced negligible further chemical alteration after early-diagenetic fossilization. These findings support previous hypotheses that fossils that display low trace element uptake are favorable targets for paleomolecular analyses.

Taphonomic and Diagenetic Pathways to Protein Preservation, Part II: The Case of Brachylophosaurus canadensis Specimen MOR 2598.

Recent recoveries of peptide sequences from two Cretaceous dinosaur bones require paleontologists to rethink traditional notions about how fossilization occurs. As part of this shifting paradigm, several research groups have recently begun attempting to characterize biomolecular decay and stabilization pathways in diverse paleoenvironmental and diagenetic settings. To advance these efforts, we assessed the taphonomic and geochemical history of Brachylophosaurus canadensis specimen MOR 2598, the left femur of which was previously found to retain endogenous cells, tissues, and structural proteins. Combined stratigraphic and trace element data show that after brief fluvial transport, this articulated hind limb was buried in a sandy, likely-brackish, estuarine channel. During early diagenesis, percolating groundwaters stagnated within the bones, forming reducing internal microenvironments. Recent exposure and weathering also caused the surficial leaching of trace elements from the specimen. Despite these shifting redox regimes, proteins within the bones were able to survive through diagenesis, attesting to their remarkable resiliency over geologic time. Synthesizing our findings with other recent studies reveals that oxidizing conditions in the initial ~48 h postmortem likely promote molecular stabilization reactions and that the retention of early-diagenetic trace element signatures may be a useful proxy for molecular recovery potential.

Taphonomic and Diagenetic Pathways to Protein Preservation, Part I: The Case of Tyrannosaurus rex Specimen MOR 1125.

Many recent reports have demonstrated remarkable preservation of proteins in fossil bones dating back to the Permian. However, preservation mechanisms that foster the long-term stability of biomolecules and the taphonomic circumstances facilitating them remain largely unexplored. To address this, we examined the taphonomic and geochemical history of Tyrannosaurus rex specimen Museum of the Rockies (MOR) 1125, whose right femur and tibiae were previously shown to retain still-soft tissues and endogenous proteins. By combining taphonomic insights with trace element compositional data, we reconstruct the postmortem history of this famous specimen. Our data show that following prolonged, subaqueous decay in an estuarine channel, MOR 1125 was buried in a coarse sandstone wherein its bones fossilized while interacting with oxic and potentially brackish early-diagenetic groundwaters. Once its bones became stable fossils, they experienced minimal further chemical alteration. Comparisons with other recent studies reveal that oxidizing early-diagenetic microenvironments and diagenetic circumstances which restrict exposure to percolating pore fluids elevate biomolecular preservation potential by promoting molecular condensation reactions and hindering chemical alteration, respectively. Avoiding protracted interactions with late-diagenetic pore fluids is also likely crucial. Similar studies must be conducted on fossil bones preserved under diverse paleoenvironmental and diagenetic contexts to fully elucidate molecular preservation pathways.

Genetics, Age and Crystallization History of Group IIC Iron Meteorites.

The eight iron meteorites currently classified as belonging to the IIC group were characterized with respect to the compositions of 21 siderophile elements. Several of these meteorites were also characterized for mass independent isotopic compositions of Mo, Ru and W. Chemical and isotopic data for one, Wiley, indicate that it is not a IIC iron meteorite and should be reclassified as ungrouped. The remaining seven IIC iron meteorites exhibit broadly similar bulk chemical and isotopic characteristics, consistent with an origin from a common parent body. Variations in highly siderophile element (HSE) abundances among the members of the group can be well accounted for by a fractional crystallization model with all the meteorites crystallizing between ~10 and ~26% of the original melt, assuming initial S and P concentrations of 8 wt.% and 2 wt.%, respectively. Abundances of HSE estimated for the parental melt suggest a composition with chondritic relative abundances of HSE ~6 times higher than in bulk carbonaceous chondrites, consistent with the IIC irons sampling a parent body core comprising ~17% of the mass of the body. Radiogenic 182W abundances of two group IIC irons, corrected for a nucleosynthetic component, indicate a metal-silicate segregation age of 3.2 ± 0.5 Myr subsequent to the formation of Calcium-Aluminum-rich Inclusions (CAI). When this age is coupled with thermal modeling, and assumptions about the Hf/W of precursor materials, a parent body accretion age of 1.4 ± 0.5 Myr (post-CAI) is obtained. The IIC irons and Wiley have 100Ru mass independent "genetic" isotopic compositions that are identical to other irons with so-called carbonaceous chondrite (CC) type genetic affinities, but enrichments in 94,95,97Mo and 183W that indicate greater s-process deficits relative to most known CC iron meteorites. If the IIC irons and Wiley are of the CC type, this indicates variable s-process deficits within the CC reservoir, similar to the s-process variability within the NC reservoir observed for iron meteorites. Nucleosynthetic models indicate that Mo and 183W s-process variability should correlate with Ru isotopic variability, which is not observed. This may indicate the IIC irons and Wiley experienced selective thermal processing of nucleosynthetic carriers, or are genetically distinct from the CC and NC precursor materials.

Origin and Age of Metal Veins in Canyon Diablo Graphite Nodules.

Previous studies attributed the origin of metal veins penetrating graphite nodules in the Canyon Diablo IAB main group iron meteorite to condensation from vapor or melting of host metal. Abundances of 16 siderophile elements measured in kamacite within vein and host meteorite are most consistent with an origin by melting of the host metal followed by fractional crystallization of the liquid. The presence of the veins within graphite nodules may be explained by impact, as peak shock temperatures, and thus the most likely areas to undergo metal melting, are at metal-graphite interfaces. The origin of the veins is constrained by Re-Os chronometry to have occurred early (>4 Ga) in Solar System history.

Molecular tests support the viability of rare earth elements as proxies for fossil biomolecule preservation.

The rare earth element (REE) composition of a fossil bone reflects its chemical alteration during diagenesis. Consequently, fossils presenting low REE concentrations and/or REE profiles indicative of simple diffusion, signifying minimal alteration, have been proposed as ideal candidates for paleomolecular investigation. We directly tested this prediction by conducting multiple biomolecular assays on a well-preserved fibula of the dinosaur Edmontosaurus from the Cretaceous Hell Creek Formation previously found to exhibit low REE concentrations and steeply-declining REE profiles. Gel electrophoresis identified the presence of organic material in this specimen, and subsequent immunofluorescence and enzyme-linked immunosorbant assays identified preservation of epitopes of the structural protein collagen I. Our results thereby support the utility of REE profiles as proxies for soft tissue and biomolecular preservation in fossil bones. Based on considerations of trace element taphonomy, we also draw predictions as to the biomolecular recovery potential of additional REE profile types exhibited by fossil bones.

Experimental Partitioning of Trace Elements into Schreibersite with Applications to IIG Iron Meteorites.

Some of the defining characteristics of the IIG iron meteorite group are their high bulk P contents and massive, coarse schreibersite, which have been calculated to make up roughly 11-14 wt% of each specimen. In this study, we produced two datasets to investigate the formation of schreibersites in IIG irons: measurements of trace elements in the IIG iron meteorite Twannberg and experimental determinations of trace element partitioning into schreibersite. The schreibersite-bearing experiments were conducted with schreibersite in equilibrium with a P-rich melt and with bulk Ni contents ranging from 0-40 wt%. The partitioning behavior for the 20 elements measured in this study did not vary with Ni content. Comparison of the Twannberg measurements with the experimental results required a correction factor to account for the fact that the experiments were conducted in a simplified system that did not contain a solid metal phase. Previously determined solid metal/P-rich melt partition coefficients were applied to infer schreibersite/solid metal partitioning behavior from the experiments, and once this correction was applied, the two datasets showed broad similarities between the schreibersite/solid metal distribution of elements. However, there were also differences noted, in particular between the Ni and P contents of the solid metal relative to the schreibersite inferred from the experiments compared to that measured in the Twannberg sample. These differences support previous interpretations that subsolidus schreibersite evolution has strongly influenced the Ni and P content now present in the solid metal phase of IIG irons. Quantitative attempts to match the IIG solid metal composition to that of late-stage IIAB irons through subsolidus schreibersite growth were not successful, but qualitatively, this study corroborates the striking similarities between the IIAB and IIG groups, which are highly suggestive of a possible genetic link between the groups as has been previously proposed.

Drawing with Iron on a Gel Containing a Supramolecular Siderophore.

Guanosine-5'-hydroxamic acid (3) forms hydrogels when mixed with guanosine (1) and KCl. The 5'-hydroxamic acid (HA) unit is pH-responsive and also chelates Fe3+ . When gels are prepared under basic conditions, the 5'-HA groups are deprotonated and the anionic hydrogel binds cationic thiazole orange (TO), signaled by enhanced fluorescence. The HA nucleoside 3, when immobilized in the G-quartet gel, acts as a supramolecular siderophore to form red complexes with Fe3+ . We patterned the hydrogel's surface with FeCl3 , by hand and by using a 3D printer. Patterns form instantly, are visible by eye, and can be erased using vitamin C. This hydrogel, combining self-assembled G-quartet and siderophore-Fe3+ motifs, is strong, can be molded into different shapes, and is stable on the bench or under salt water.

Experimental Determination of Partitioning in the Fe-Ni System for Applications to Modeling Meteoritic Metals.

Experimental trace element partitioning values are often used to model the chemical evolution of metallic phases in meteorites, but limited experimental data were previously available to constrain the partitioning behavior in the basic Fe-Ni system. In this study, we conducted experiments that produced equilibrium solid metal and liquid metal phases in the Fe-Ni system and measured the partition coefficients of 25 elements. The results are in good agreement with values modeled from IVB iron meteorites and with the limited previous experimental data. Additional experiments with low levels of S and P were also conducted, to help constrain the partitioning behaviors of elements as a function of these light elements. The new experimental results were used to derive a set of parameterization values for element solid metal-liquid metal partitioning behavior in the Fe-Ni-S, Fe-Ni-P, and Fe-Ni-C ternary systems at 0.1 MPa. The new parameterizations require that the partitioning behaviors in the light-element-free Fe-Ni system are those determined experimentally by this study, in contrast to previous parameterizations that allowed this value to be determined as a best-fit parameter. These new parameterizations, with self-consistent values for partitioning in the end-member Fe-Ni system, provide a valuable resource for future studies that model the chemical evolution of metallic phases in meteorites.

Diverse impactors in Apollo 15 and 16 impact melt rocks: evidence from osmium isotopes and highly siderophile elements.

Concentrations of highly siderophile elements (HSE) and 187Os/188Os isotopic compositions for eleven impact related rocks from the Apollo 15 and 16 landing sites are reported and combined with existing geochronological data to investigate the chemical nature and temporal changes in the large impactors implicated in the formation of the lunar basins. Data for the samples all define linear trends on plots of HSE versus Ir concentrations, whose slopes likely reflect the relative HSE compositions of the dominant impactors that formed the rocks. The inferred Imbrium basin impactor that generated Apollo 15 impact melt rocks 15445 and 15455 was characterized by modestly suprachondritic 187Os/188Os, Ru/Ir, Pt/Ir and Pd/Ir ratios. Diverse impactor components are revealed in the Apollo 16 impact melt rocks. The 187Os/188Os and HSE/Ir ratios of the impactor components in melt rocks 60635, 63595 and 68416, with reported ages < 3.84 Ga, are within the range of chondritic meteorites, but slightly higher than ratios characterizing previously studied granulitic impactites with reported ages > 4.0 Ga. By contrast, the impactor components in melt rocks 60235, 62295 and 67095, with reported ages of ~3.9 Ga, are characterized by suprachondritic 187Os/188Os and HSE/Ir ratios similar to the Apollo 15 impact melt rocks, and may also sample the Imbrium impactor. Three lithic clasts from regolith breccias 60016 and 65095, also with ~3.9 Ga ages, contain multiple impactor components, of which the dominant composition is considerably more suprachondritic than those implicated for Imbrium and Serenitatis (Apollo 17) impactors. The dominant composition recorded in these rocks was most likely inherited from a pre-Imbrium impactor. Consideration of composition versus age relations among lunar impact melt rocks reveals no discernable trend. Virtually all lunar impact melt rocks sampled by the Apollo missions, as well as meteorites, are characterized by 187Os/188Os and HSE/Ir ratios that, when collectively plotted, define linear trends ranging from chondritic to fractionated compositions. The impact melt rocks with HSE signatures within the range of chondritic meteorites are interpreted to have been derived from impactors that had HSE compositions similar to known chondrite groups. By contrast, the impact melt rocks with non-chondritic relative HSE concentrations could not have been made by mixing of known chondritic impactors. These signatures may instead reflect contributions from early solar system bodies with bulk chemical compositions that have not yet been sampled by primitive meteorites present in our collections. Alternately, they may reflect the preferential incorporation of evolved metal separated from a fractionated planetesimal core. Pre-3.9 Ga ages for at least some impactor components with both chondritic and fractionated HSE raise the possibility that the bulk of the HSE were added to the lunar crust prior to the later-stage basin-forming impacts, such as Imbrium and Serenitatis, as proposed by Fischer-Gödde and Becker (2012). For this scenario, the later-stage basin-forming impacts were more important with respect to mixing prior impactor components into melt rocks, rather than contributing much to the HSE budgets of the rocks themselves.

Early formation of evolved asteroidal crust.

Mechanisms for the formation of crust on planetary bodies remain poorly understood. It is generally accepted that Earth's andesitic continental crust is the product of plate tectonics, whereas the Moon acquired its feldspar-rich crust by way of plagioclase flotation in a magma ocean. Basaltic meteorites provide evidence that, like the terrestrial planets, some asteroids generated crust and underwent large-scale differentiation processes. Until now, however, no evolved felsic asteroidal crust has been sampled or observed. Here we report age and compositional data for the newly discovered, paired and differentiated meteorites Graves Nunatak (GRA) 06128 and GRA 06129. These meteorites are feldspar-rich, with andesite bulk compositions. Their age of 4.52 +/- 0.06 Gyr demonstrates formation early in Solar System history. The isotopic and elemental compositions, degree of metamorphic re-equilibration and sulphide-rich nature of the meteorites are most consistent with an origin as partial melts from a volatile-rich, oxidized asteroid. GRA 06128 and 06129 are the result of a newly recognized style of evolved crust formation, bearing witness to incomplete differentiation of their parent asteroid and to previously unrecognized diversity of early-formed materials in the Solar System.

ATM-mediated transcriptional elevation of prion in response to copper-induced oxidative stress.

Increasing evidence suggests that the cellular prion protein (PrP(C)) plays a protective role in response to oxidative stress, but the molecular mechanism is unclear. Here, we demonstrate that murine neuro-2a and human HeLa cells rapidly respond to an increase of intracellular copper concentration by up-regulating ataxia-telangiectasia mutated (ATM)-mediated transcription of PrP(C). Copper stimulation activates ATM by phosphorylation at Ser-1981, which leads to phosphorylation of p53 at Ser-15 and the initiation of the mitogen-activated protein kinase kinase/extracellular-related kinases/extracellular-related kinases (MEK/ERK)/Sp1 pathway. As results, Sp1 and p53 bind to the PrP promoter, leading to increase PrP(C) expression. Elevated PrP(C) correlates with reduction of intracellular copper concentration and suppression of Cu(II)-induced accumulation of reactive oxygen species and cell death. Depletion of PrP(C), ATM, p53, and/or Sp1 further demonstrates that ATM is a key regulatory protein to promote activation of p53 and Sp1 leading to PrP(C) elevation, which is required to reduce Cu(II) toxic effects and may play an important role in modulation of intracellular copper concentration.