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Initial analyses showed that asteroid Ryugu's composition is close to CI (Ivuna-like) carbonaceous chondrites (CCs) - the chemically most primitive meteorites, characterized by near-solar abundances for most elements. However, some isotopic signatures (for example, Ti, Cr) overlap with other CC groups, so the details of the link between Ryugu and the CI chondrites are not yet fully clear. Here we show that Ryugu and CI chondrites have the same zinc and copper isotopic composition. As the various chondrite groups have very distinct Zn and Cu isotopic signatures, our results point at a common genetic heritage between Ryugu and CI chondrites, ruling out any affinity with other CC groups. Since Ryugu's pristine samples match the solar elemental composition for many elements, their Zn and Cu isotopic compositions likely represent the best estimates of the solar composition. Earth's mass-independent Zn isotopic composition is intermediate between Ryugu/CC and non-carbonaceous chondrites (NCs), suggesting a contribution of Ryugu-like material to Earth's budgets of Zn and other moderately volatile elements.

Correction to: Nature Astronomy https://doi.org/10.1038/s41550-022-01846-1. Published online 12 December 2022.

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 5.2 − 0.7 + 0.8 million (statistical) or 5.2 − 2.1 + 1.6 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.

We performed micro-X-ray fluorescence imaging of frozen-hydrated sections of a root of Pteris vittata for the first time, to the best of our knowledge, to reveal the mechanism of arsenic (As) uptake. The As distribution was successfully visualized in cross sections of different parts of the root, which showed that (i) the major pathway of As uptake changes from symplastic to apoplastic transport in the direction of root growth, and (ii) As and K have different mobilities around the stele before xylem loading, despite their similar distributions outside the stele in the cross sections. These data can reasonably explain As reduction, axially observed around the root tip in the direction of root growth and radially observed in the endodermis in the cross sections, as a consequence of the incorporation of As into the cells or symplast of the root. In addition, previous observations of As species in the midrib can be reconciled by ascribing a reduction capacity to the root cells, which implies that As reduction mechanisms at the cellular level may be an important control on the peculiar root-to-shoot transport of As in P. vittata.

The striking sub-cellular distribution of cadmium (Cd) and zinc (Zn) in the Cd and Zn hyperaccumulator Arabidopsis halleri ssp. gemmifera was revealed by microbeam X-ray microfluorescence analysis (μ-XRF) using high-energy synchrotron radiation. Plants were grown in hydroponics with various Cd and Zn concentrations. The concentration of Cd in the aerial portions of the plants increased with increasing Zn exposure and the transportation efficiency of Cd from the root to the shoot was affected by both the Cd and Zn concentrations in the nutrient solution. The μ-XRF imaging clearly showed that Cd and Zn were preferentially accumulated in trichomes on the leaf, while the distribution of Cd in the leaf was changed by Zn treatment. It was observed that Cd treated with a higher Zn concentration (20 μM Cd + 100 μM Zn) was distributed in the mesophyll tissue at high concentrations. In addition, μ-XRF imaging clarified that the distribution of Zn inside the leaf was different from that of Cd at a cellular level. Zn was primarily distributed in the mesophyll tissue of the leaf blade. In contrast, Cd was localized in the vascular bundle of the main vein. That is, Zn was transported to mesophyll tissue from the vascular bundle more efficiently than Cd. As seen above, we were able to study the difference of the distribution of Cd and Zn, which are congeners and behave similarly, inside the plant body at the cellular level in detail by high-energy μ-XRF.

In 1964, a fragment of a colorless facet-cut glass vessel was collected at the Kamigamo Shrine, located in Kyoto, which was the capital city of Japan from late 8th century AD through the mid-19th century AD. X-ray fluorescence analytical techniques were applied to this fragment in a nondestructive manner with the aim of scientific provenancing based on its chemical compositional features. It was found that, the chemical composition of the fragment closely matched that of one compositional group in Sasanian glass which was characterized by the use of a pure silica source and magnesia-rich plant ash as the raw materials. Given the discoveries of facet-cut glassware from the region of the Sasanian Empire that are very similar to this fragment, it is concluded that the primary production and possibly subsequent production processes (i.e., secondary production and a facet-cut decoration) of this glass were carried out at the Sasanian glass workshops. This study is the second case of an investigation that has identified a specific provenance of one of the few glass vessels introduced into ancient Japan through the Silk Road.

X-ray fluorescence analytical techniques were applied to two pieces of glass fragments because they are believed to be sampled from two pieces of important glassware, a facet-cut bowl and a deeply-blue colored dish, excavated from Niizawa Senzuka Tumulus No.126, Nara, Japan (late 5th century). Two different provenances were estimated as primary production area for the two glass fragments. One fragment has a chemical composition being a good match with that of Sasanian glass excavated at Veh Ardasīr in central Iraq. Conversely, composition of another fragment is consistent with common blue-green colored Roman glass manufactured during the imperial period. If these glass fragments are actually identical to the ancient glassware excavated from Nara, our results can provide scientific evidence how various cultures were introduced to and accepted by ancient Japan. Concomitantly, they are also evidence of an extremely widespread Silk Road trading from the Mediterranean and West Asia to the Far East of Japan during the 1st millennium AD.

Synchrotron μ-XRF and autoradiography complementally revealed the different behavior of arsenic and phosphorus in Pteris vittata L. at a high spatial resolution in its living state. We found that P...

The use of a portable X-ray fluorescence spectrometer revealed the provenance of a shard of a relief-cut glass bowl which was dedicated to ancient ritual on the sacred island of Okinoshima, Japan over a thousand years ago. The shard was unearthed from one of the ritual sites on the island in the 1950s and is now designated as a national treasure in Japan. A nondestructive and on-site X-ray fluorescence analytical technique was applied to the Okinoshima glass shard to establish where and when it was originally manufactured based on its chemical composition. Clear correspondence of chemical composition between the shard and glass excavated from a Sasanian city site in Mesopotamia demonstrated that the shard was derived from a type of glassware primarily produced in glass workshops within the Sasanian Empire between the fifth and seventh centuries AD. This is the first scientific evidence demonstrating that glass was imported from overseas across thousands of kilometers and then dedicated for the ritual on Okinoshima Island. This simultaneously gives us a glimpse of the specific details of divine rituals conducted on Okinoshima Island in ancient times.

A portable X-ray powder diffractometer (p-XRD) PT-APXRD III has been developed for onsite analysis of paintings and archaeological samples. By using a Cu anode X-ray tube and a silicon drift diode (SDD) detector, diffraction patterns with a high signalnoise (S/N) ratio can be recorded. The X-ray tube can be operated at a maximum voltage of 60 kV, which makes it possible to simultaneously record X-ray fluorescence spectra up to the high-energy region. The total weight of this instrument is 16 kg, which can be carried anywhere and the goniometer unit (5.6 kg) can be placed on a tripod for analysis of mural paintings. We brought the instrument to the Rijksmuseum in the Netherlands to examine its applicability for the analysis of oil paintings. We successfully analyzed two seventeenthcentury oil paintings by Johannes Vermeer and Jan Davidsz de Heem (copy after). Ultramarine blue, leadtin yellow type I, and Naples yellow were identified from the diffraction patterns, demonstrating the high practicality of this instrument. Furthermore, it was found from the SEM-EDX analysis of a paint cross section that the yellow pigment was applied in separate layers rather than being mixed. This diffractometer will be commercially available in the near future and will have many applications in the field of material analysis. (C) 2018 Elsevier B.V. All rights reserved.

Mn-bearing hellandite-(Y) occurs as pinkish yellow granular crystals (up to sub mm) in the Sc-rich granite pegmatite at Heftetjern, Tordal, Telemark, Norway. Associated minerals are quartz, albite, Sc- and Ce-bearing epidote, hingganite-(Y), and an undetermined Ca-bearing hingganite-related mineral. Electron microprobe analyses give an empirical formula as Ca1.34Mn1.07Y2.75Ce0.02Nd0.02Sm0.01Gd0.01Dy0.05Er0.05Yb0.15Al0.94Fe0.08Si3.99B4.33O22.00(OH)2.00 on the basis of Al+Fe+Si = 5 and 24 anions per formula unit. The lattice parameters were refined from diffraction data obtained using a Gandolfi camera with an imaging plate and Ni filtered Cu K α; a 18.693(17), b 4.651(3), c 10.178(7) A, β = 111.37(6)°, V 824.1(10) A3. The crystal structure was refined from single-crystal XRD data obtained with a CCD-diffractometer and graphite-monochromated Mo K α. The refinement with anisotropic atomic displacement parameters converged to R 1 = 0.0269 for 1567 reflections [ I > 2σ( I )] and 0.0318 for all 1768 reflections, resulting in the structural formula M 3(Ca0.56Mn0.44)2 M 4(Y0.43Ca0.23Ln0.14□ 0.20)2 M 2(Y0.94Ln0.06)2 M 1(Al0.92Fe0.08)Si4B4O21.21(OH)2.79. In this hellandite-(Y), Mn2+ replaces Ca2+ at the M 3 site and there is a significant vacancy at the M 4 site. The T site is vacant, and, instead, the O5 position is occupied by (OH)–.

This paper reports on how the application of macro X-ray fluorescence (MA-XRF) imaging, in combination with the re-examination of existing paint cross-sections, has led to the discovery of a new pigment in Rembrandt’s palette: artificial orpiment. In the NWO Science4Arts ‘ReVisRembrandt’ project, novel chemical imaging techniques are being developed and applied to the study of Rembrandt’s late paintings in order to help resolve outstanding questions and to gain a better understanding of his late enigmatic painting technique. One of the selected case studies is the Portrait of a Couple as Isaac and Rebecca, known as ‘The Jewish Bride’, dated c. 1665 and on view in the Rijksmuseum. During the re-installation of the Rijksmuseum in 2013, the picture was scanned using the Bruker M6 Jetstream MA-XRF scanner. The resulting elemental distribution maps made it possible to distinguish many features in the painting, such as bone black remains of the original hat (P, Ca maps), and the now discolored smalt-rich background (Co, Ni, As, K maps). The arsenic (As) map also revealed areas of high-intensity in Isaac’s sleeve and Rebecca’s dress where it could be established that it was not related with the pigment smalt that also contains arsenic. This pointed to the presence of a yellow or orange arsenic-containing pigment, such as realgar or orpiment that is not associated with the artist’s palette. Subsequent examination of existing paint cross-sections from these locations taken by Karin Groen in the 1990s identified isolated, almost perfectly round particles of arsenic sulfide. The round shape corresponds with published findings on a purified form of artificial orpiment glass obtained by dry processing, a sublimation reaction. In bright field, the particles characteristically exhibit a dark cross in the middle caused by internal light reflections. The results of additional non-invasive techniques (portable XRD and portable Raman) are discussed, as well as the implications of this finding and how it fits with Rembrandt’s late experimental painting technique.

Synchrotron radiation (SR) X-ray microbeam analyses revealed the detailed chemical nature of radioactive aerosol microparticles emitted during the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, resulting in better understanding of what occurred in the plant during the early stages of the accident. Three spherical microparticles (∼2 μm, diameter) containing radioactive Cs were found in aerosol samples collected on March 14th and 15th, 2011, in Tsukuba, 172 km southwest of the FDNPP. SR-μ-X-ray fluorescence analysis detected the following 10 heavy elements in all three particles: Fe, Zn, Rb, Zr, Mo, Sn, Sb, Te, Cs, and Ba. In addition, U was found for the first time in two of the particles, further confirmed by U L-edge X-ray absorption near-edge structure (XANES) spectra, implying that U fuel and its fission products were contained in these particles along with radioactive Cs. These results strongly suggest that the FDNPP was damaged sufficiently to emit U fuel and fission products outside the containment vessel as aerosol particles. SR-μ-XANES spectra of Fe, Zn, Mo, and Sn K-edges for the individual particles revealed that they were present at high oxidation states, i.e., Fe(3+), Zn(2+), Mo(6+), and Sn(4+) in the glass matrix, confirmed by SR-μ-X-ray diffraction analysis. These radioactive materials in a glassy state may remain in the environment longer than those emitted as water-soluble radioactive Cs aerosol particles.

Variscite is a green, lustrous mineral similar to turquoise. While both variscite and turquoise are aluminum-bearing, hydrated phosphate minerals, variscite contains no copper. We applied three kinds of portable analytical instruments to a nondestructive, on-site analysis of Late Bronze Age (LBA) artifacts excavated from a royal tomb at Qatna, Syria, including a portable micro-Raman spectrometer, an X-ray powder diffractometer, and an X-ray fluorescence spectrometer. Variscite was positively identified as the raw material for a number of items from the Qatna tomb. Our analytical result is the first scientific evidence of the use of variscite for personal ornaments during the LBA in the Middle East. Because differentiating between variscite and turquoise is difficult with the naked eye, it is possible that variscite artifacts were misidentified as turquoise among Middle Eastern LBA items excavated from other archaeological sites.

We have started to construct a nationwide forensic soil sediment database for Japan, based on the heavy mineral and trace heavy element compositions of stream sediments collected at 3024 points across Japan. The data were measured by high-resolution synchrotron radiation X-ray powder diffraction (SR-XRD) and high-energy SR X-ray fluorescence analysis (XRF) using the SR source of SPring-8, the SR radiation facility in Japan. The automated sampling systems allow the measurement of 130 powder diffraction patterns and 100 XRF spectra per day using sediment samples of just a few milligrams, which enabled us to construct a database of a large number of samples. The concentrations of heavy elements such as rare earth elements, Cs and W up to 500 ppm level in soil sediments can be determined by the calibration curve method by using high-energy SR-XRF utilizing monochromatic X-rays of 116 keV. A heavy element concentration map superimposed on a geographical map of Japan was successfully prepared from these analytical data. The heavy mineral compositions were quantitatively evaluated by using the peak intensity of characteristic XRD peaks of the component minerals measured by a Debye–Scherrer camera having a radius of 286.5 mm, recorded with an imaging plate and monochromatic X-rays (λ = 1.0 A). This study demonstrates that XRF and XRD data collected from the sediments of Shizuoka Prefecture closely reflect the geological and geographical signature of the sediment samples, which can be used for the provenance determination of soil evidence from a crime scene. Copyright © 2013 John Wiley & Sons, Ltd.

Gynura pseudochina (L.) DC. is a zinc (Zn)/cadmium (Cd) hyperaccumulative plant. The aim of this study was to examine the tolerance of G. pseudochina (L.) DC. for Zn and/or Cd accumulation and protein expression. An in vitro tissue culture system was used to control the environment and effects of the microorganisms. Treatments with higher Zn and Cd concentrations increased chlorosis and the accumulation of metals in the root and shoot. Cd treatment at low levels induced the growth of the plant, and the translocation factor was high. A dual treatment with Cd and Zn decreased the metals’ toxicity and demonstrated the plant’s proclivity to accumulate Cd. The SDS–PAGE and FT-IR analyses showed the effect of the metals’ toxicity on protein expression and secondary structure. Moreover, using XAFS techniques, it was demonstrated that treatment with a high Zn concentration (100 mg l −1 ) resulted in tetrahedral coordination with mixed S/O ligation in the protein extract as compared with Zn O coordination in the protein extract from the control plant cultured in the presence of trace levels of Zn (0.04 mg l −1 ). This research suggested that G. pseudochina (L.) DC. had properties to tolerate a high Zn and Cd concentration, related to the sulphur proteins.