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1.
Anal Chem ; 96(1): 170-178, 2024 Jan 09.
Article in English | MEDLINE | ID: mdl-38155534

ABSTRACT

Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca2+ and Mn2+ on the Mg2+- and Fe2+-rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca2+, Mg2+, and Fe2+ + Mn2+) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe2+ + Mn2+ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy-energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.

2.
Sci Adv ; 9(45): eadi7048, 2023 Nov 10.
Article in English | MEDLINE | ID: mdl-37939187

ABSTRACT

Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between 54Cr-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred [Formula: see text] after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water.

3.
Sci Adv ; 9(28): eadh1003, 2023 Jul 14.
Article in English | MEDLINE | ID: mdl-37450600

ABSTRACT

Preliminary analyses of asteroid Ryugu samples show kinship to aqueously altered CI (Ivuna-type) chondrites, suggesting similar origins. We report identification of C-rich, particularly primitive clasts in Ryugu samples that contain preserved presolar silicate grains and exceptional abundances of presolar SiC and isotopically anomalous organic matter. The high presolar silicate abundance (104 ppm) indicates that the clast escaped extensive alteration. The 5 to 10 times higher abundances of presolar SiC (~235 ppm), N-rich organic matter, organics with N isotopic anomalies (1.2%), and organics with C isotopic anomalies (0.2%) in the primitive clasts compared to bulk Ryugu suggest that the clasts formed in a unique part of the protoplanetary disk enriched in presolar materials. These clasts likely represent previously unsampled outer solar system material that accreted onto Ryugu after aqueous alteration ceased, consistent with Ryugu's rubble pile origin.


Subject(s)
Carbon , Meteoroids , Carbon/analysis , Solar System , Silicates
4.
Science ; 379(6634): eabn7850, 2023 Feb 24.
Article in English | MEDLINE | ID: mdl-35679354

ABSTRACT

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about [Formula: see text] million (statistical) or [Formula: see text] million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun's photosphere than other natural samples do.

5.
Sci Adv ; 8(50): eade2067, 2022 Dec 16.
Article in English | MEDLINE | ID: mdl-36525483

ABSTRACT

The extraterrestrial materials returned from asteroid (162173) Ryugu consist predominantly of low-temperature aqueously formed secondary minerals and are chemically and mineralogically similar to CI (Ivuna-type) carbonaceous chondrites. Here, we show that high-temperature anhydrous primary minerals in Ryugu and CI chondrites exhibit a bimodal distribution of oxygen isotopic compositions: 16O-rich (associated with refractory inclusions) and 16O-poor (associated with chondrules). Both the 16O-rich and 16O-poor minerals probably formed in the inner solar protoplanetary disk and were subsequently transported outward. The abundance ratios of the 16O-rich to 16O-poor minerals in Ryugu and CI chondrites are higher than in other carbonaceous chondrite groups but are similar to that of comet 81P/Wild2, suggesting that Ryugu and CI chondrites accreted in the outer Solar System closer to the accretion region of comets.

6.
Sci Adv ; 8(46): eadd8141, 2022 Nov 18.
Article in English | MEDLINE | ID: mdl-36264823

ABSTRACT

Little is known about the origin of the spectral diversity of asteroids and what it says about conditions in the protoplanetary disk. Here, we show that samples returned from Cb-type asteroid Ryugu have Fe isotopic anomalies indistinguishable from Ivuna-type (CI) chondrites, which are distinct from all other carbonaceous chondrites. Iron isotopes, therefore, demonstrate that Ryugu and CI chondrites formed in a reservoir that was different from the source regions of other carbonaceous asteroids. Growth and migration of the giant planets destabilized nearby planetesimals and ejected some inward to be implanted into the Main Belt. In this framework, most carbonaceous chondrites may have originated from regions around the birthplaces of Jupiter and Saturn, while the distinct isotopic composition of CI chondrites and Ryugu may reflect their formation further away in the disk, owing their presence in the inner Solar System to excitation by Uranus and Neptune.

7.
Nat Commun ; 11(1): 5027, 2020 10 06.
Article in English | MEDLINE | ID: mdl-33024094

ABSTRACT

Few palaeoclimate archives beyond the polar regions preserve continuous and datable palaeotemperature proxy time series over multiple glacial-interglacial cycles. This hampers efforts to develop a more coherent picture of global patterns of past temperatures. Here we show that Mg concentrations in a subaqueous speleothem from an Italian cave track regional sea-surface temperatures over the last 350,000 years. The Mg shows higher values during warm climate intervals and converse patterns during cold climate stages. In contrast to previous studies, this implicates temperature, not rainfall, as the principal driver of Mg variability. The depositional setting of the speleothem gives rise to Mg partition coefficients that are more temperature dependent than other calcites, enabling the effect of temperature change on Mg partitioning to greatly exceed the effects of changes in source-water Mg/Ca. Subaqueous speleothems from similar deep-cave environments should be capable of providing palaeotemperature information over multiple glacial-interglacial cycles.

8.
Proc Natl Acad Sci U S A ; 116(38): 18854-18859, 2019 09 17.
Article in English | MEDLINE | ID: mdl-31481607

ABSTRACT

Atmospheric oxygen has evolved from negligible levels in the Archean to the current level of about 21% through 2 major step rises: The Great Oxidation Event (GOE) in the early Proterozoic and the Neoproterozoic Oxygenation Event (NOE) during the late Proterozoic. However, most previous methods for constraining the time of atmospheric oxygenation have relied on evidence from sedimentary rocks. Here, we investigate the temporal variations of the Th/U of arc igneous rocks since 3.0 billion y ago (Ga) and show that 2 major Th/U decreases are recorded at ca. 2.35 Ga and ca. 0.75 Ga, coincident with the beginning of the GOE and NOE. The decoupling of U from Th is predominantly caused by the significant rise of atmospheric oxygen. Under an increasingly oxidized atmosphere condition, more uranium in the surface environment became oxidized from the water-insoluble U4+ to the water-soluble U6+ valance and incorporated in the sea water and altered oceanic crust. Eventually, the subduction of this altered oceanic crust produced the low-Th/U signature of arc igneous rocks. Therefore, the sharp decrease of Th/U in global arc igneous rocks may provide strong evidence for the rise of atmospheric oxygen. We suggest that the secular Th/U evolution of arc igneous rocks could be an effective geochemical indicator recording the global-scale atmospheric oxygen variation.

9.
Nat Commun ; 9(1): 2245, 2018 06 08.
Article in English | MEDLINE | ID: mdl-29884814

ABSTRACT

The Great Oxidation Event (GOE) has been defined as the time interval when sufficient atmospheric oxygen accumulated to prevent the generation and preservation of mass-independent fractionation of sulphur isotopes (MIF-S) in sedimentary rocks. Existing correlations suggest that the GOE was rapid and globally synchronous. Here we apply sulphur isotope analysis of diagenetic sulphides combined with U-Pb and Re-Os geochronology to document the sulphur cycle evolution in Western Australia spanning the GOE. Our data indicate that, from ~2.45 Gyr to beyond 2.31 Gyr, MIF-S was preserved in sulphides punctuated by several episodes of MIF-S disappearance. These results establish the MIF-S record as asynchronous between South Africa, North America and Australia, argue for regional-scale modulation of MIF-S memory effects due to oxidative weathering after the onset of the GOE, and suggest that the current paradigm of placing the GOE at 2.33-2.32 Ga based on the last occurrence of MIF-S in South Africa should be re-evaluated.

10.
Rev Sci Instrum ; 84(1): 011101, 2013 Jan.
Article in English | MEDLINE | ID: mdl-23387630

ABSTRACT

Mass spectrometry is fundamental to measurements of isotope ratios for applications in isotope geochemistry, geochronology, and cosmochemistry. Magnetic-sector mass spectrometers are most common because these provide the best precision in isotope ratio measurements. Where the highest precision is desired, chemical separation followed by mass spectrometric analysis is carried out with gas (noble gas and stable isotope mass spectrometry), liquid (inductively coupled plasma mass spectrometry), or solid (thermal ionization mass spectrometry) samples. Developments in in situ analysis, including ion microprobes and laser ablation inductively coupled plasma mass spectrometry, have opened up issues concerning homogeneity according to domain size, and allow ever smaller amounts of material to be analyzed. While mass spectrometry is built solidly on developments in the 20th century, there are new technologies that will push the limits in terms of precision, accuracy, and sample efficiency. Developments of new instruments based on time-of-flight mass spectrometers could open up the ultimate levels of sensitivity per sample atom.

11.
Science ; 333(6046): 1116-9, 2011 Aug 26.
Article in English | MEDLINE | ID: mdl-21868668

ABSTRACT

Meteorite studies suggest that each solar system object has a unique oxygen isotopic composition. Chondrites, the most primitive of meteorites, have been believed to be derived from asteroids, but oxygen isotopic compositions of asteroids themselves have not been established. We measured, using secondary ion mass spectrometry, oxygen isotopic compositions of rock particles from asteroid 25143 Itokawa returned by the Hayabusa spacecraft. Compositions of the particles are depleted in (16)O relative to terrestrial materials and indicate that Itokawa, an S-type asteroid, is one of the sources of the LL or L group of equilibrated ordinary chondrites. This is a direct oxygen-isotope link between chondrites and their parent asteroid.

12.
Science ; 333(6046): 1125-8, 2011 Aug 26.
Article in English | MEDLINE | ID: mdl-21868671

ABSTRACT

Regolith particles on the asteroid Itokawa were recovered by the Hayabusa mission. Their three-dimensional (3D) structure and other properties, revealed by x-ray microtomography, provide information on regolith formation. Modal abundances of minerals, bulk density (3.4 grams per cubic centimeter), and the 3D textures indicate that the particles represent a mixture of equilibrated and less-equilibrated LL chondrite materials. Evidence for melting was not seen on any of the particles. Some particles have rounded edges. Overall, the particles' size and shape are different from those seen in particles from the lunar regolith. These features suggest that meteoroid impacts on the asteroid surface primarily form much of the regolith particle, and that seismic-induced grain motion in the smooth terrain abrades them over time.

13.
Science ; 333(6046): 1128-31, 2011 Aug 26.
Article in English | MEDLINE | ID: mdl-21868672

ABSTRACT

Noble gas isotopes were measured in three rocky grains from asteroid Itokawa to elucidate a history of irradiation from cosmic rays and solar wind on its surface. Large amounts of solar helium (He), neon (Ne), and argon (Ar) trapped in various depths in the grains were observed, which can be explained by multiple implantations of solar wind particles into the grains, combined with preferential He loss caused by frictional wear of space-weathered rims on the grains. Short residence time of less than 8 million years was implied for the grains by an estimate on cosmic-ray-produced (21)Ne. Our results suggest that Itokawa is continuously losing its surface materials into space at a rate of tens of centimeters per million years. The lifetime of Itokawa should be much shorter than the age of our solar system.

14.
Nature ; 440(7085): 776-8, 2006 Apr 06.
Article in English | MEDLINE | ID: mdl-16598252

ABSTRACT

Differences in isotopic abundances between meteorites and rocks on Earth leave unclear the true composition of the gas out of which the Solar System formed. The Sun should have preserved in its outer layers the original composition, and recent work has indicated that the solar wind is enriched in 16O, relative to Earth, Mars and bulk meteorites. This suggests that self-shielding of CO due to photo-dissociation, which is a well understood process in molecular clouds, also led to evolution in the isotopic abundances in the early Solar System. Here we report measurements of oxygen isotopic abundances in lunar grains that were recently exposed to the solar wind. We find that 16O is underabundant, opposite to an earlier finding based on studies of ancient metal grains. Our result, however, is more difficult to understand within the context of current models, because there is no clear way to make 16O more abundant in Solar System rocks than in the Sun.

15.
Chiropr Osteopat ; 13: 16, 2005 Aug 09.
Article in English | MEDLINE | ID: mdl-16091134

ABSTRACT

OBJECTIVE: This review details the anatomy and interactions of the postural and somatosensory reflexes. We attempt to identify the important role the nervous system plays in maintaining reflex control of the spine and posture. We also review, illustrate, and discuss how the human vertebral column develops, functions, and adapts to Earth's gravity in an upright position. We identify functional characteristics of the postural reflexes by reporting previous observations of subjects during periods of microgravity or weightlessness. BACKGROUND: Historically, chiropractic has centered around the concept that the nervous system controls and regulates all other bodily systems; and that disruption to normal nervous system function can contribute to a wide variety of common ailments. Surprisingly, the chiropractic literature has paid relatively little attention to the importance of neurological regulation of static upright human posture. With so much information available on how posture may affect health and function, we felt it important to review the neuroanatomical structures and pathways responsible for maintaining the spine and posture. Maintenance of static upright posture is regulated by the nervous system through the various postural reflexes. Hence, from a chiropractic standpoint, it is clinically beneficial to understand how the individual postural reflexes work, as it may explain some of the clinical presentations seen in chiropractic practice. METHOD: We performed a manual search for available relevant textbooks, and a computer search of the MEDLINE, MANTIS, and Index to Chiropractic Literature databases from 1970 to present, using the following key words and phrases: "posture," "ocular," "vestibular," "cervical facet joint," "afferent," "vestibulocollic," "cervicocollic," "postural reflexes," "spaceflight," "microgravity," "weightlessness," "gravity," "posture," and "postural." Studies were selected if they specifically tested any or all of the postural reflexes either in Earth's gravity or in microgravitational environments. Studies testing the function of each postural component, as well as those discussing postural reflex interactions, were also included in this review. DISCUSSION: It is quite apparent from the indexed literature we searched that posture is largely maintained by reflexive, involuntary control. While reflexive components for postural control are found in skin and joint receptors, somatic graviceptors, and baroreceptors throughout the body, much of the reflexive postural control mechanisms are housed, or occur, within the head and neck region primarily. We suggest that the postural reflexes may function in a hierarchical fashion. This hierarchy may well be based on the gravity-dependent or gravity-independent nature of each postural reflex. Some or all of these postural reflexes may contribute to the development of a postural body scheme, a conceptual internal representation of the external environment under normal gravity. This model may be the framework through which the postural reflexes anticipate and adapt to new gravitational environments. CONCLUSION: Visual and vestibular input, as well as joint and soft tissue mechanoreceptors, are major players in the regulation of static upright posture. Each of these input sources detects and responds to specific types of postural stimulus and perturbations, and each region has specific pathways by which it communicates with other postural reflexes, as well as higher central nervous system structures. This review of the postural reflex structures and mechanisms adds to the growing body of posture rehabilitation literature relating specifically to chiropractic treatment. Chiropractic interest in these reflexes may enhance the ability of chiropractic physicians to treat and correct global spine and posture disorders. With the knowledge and understanding of these postural reflexes, chiropractors can evaluate spinal configurations not only from a segmental perspective, but can also determine how spinal dysfunction may be the ultimate consequence of maintaining an upright posture in the presence of other postural deficits. These perspectives need to be explored in more detail.

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