Analysis of Cation Composition in Dolomites on the Intact Particles Sampled from Asteroid Ryugu.

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.

Water circulation in Ryugu asteroid affected the distribution of nucleosynthetic isotope anomalies in returned sample.

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.

Abundant presolar grains and primordial organics preserved in carbon-rich exogenous clasts in asteroid Ryugu.

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.

Samples returned from the asteroid Ryugu are similar to Ivuna-type carbonaceous meteorites.

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.

Ryugu's nucleosynthetic heritage from the outskirts of the Solar System.

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.

Slow Conformational Changes of Blue Light Sensor BLUF Proteins in Milliseconds.

Blue light sensor using flavin (BLUF) proteins consist of flavin-binding BLUF domains and functional domains. Upon blue light excitation, the hydrogen bond network around the flavin chromophore changes, and the absorption spectrum in the visible region exhibits a red shift. Ultimately, the light information received in the BLUF domain is transmitted to the functional region. It has been believed that this red shift is complete within nanoseconds. In this study, slow reaction kinetics were discovered in milliseconds (τ1- and τ2-phase) for all the BLUF proteins examined (AppA, OaPAC, BlrP1, YcgF, PapB, SyPixD, and TePixD). Despite extensive reports on BLUF, this is the first clear observation of the BLUF protein absorption change with the duration in the millisecond time region. From the measurements of some domain-deleted mutants of OaPAC and two chimeric mutants of PixD proteins, it was found that the slower dynamics (τ2-phase) are strongly affected by the size and nature of the C-terminal region adjacent to the BLUF domain. Hence, this millisecond reaction is a significant indicator of conformational changes in the C-terminal region, which is essential for the biological functions. On the other hand, the τ1-phase commonly exists in all BLUF proteins, including any mutants. The origin of the slow dynamics was studied using site-specific mutants. These results clearly show the importance of Trp in the BLUF domain. Based on this, a reaction scheme for the BLUF reaction is proposed.