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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.

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.

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.

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.

We have started the construction of 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 all over Japan obtained by high-resolution synchrotron X-ray powder diffraction (SR-XRD) and high-energy synchrotron X-ray fluorescence analysis (HE-SR-XRF). In this study, the performance of both techniques was demonstrated by analyzing soil sediments from two different geological regions, the Kofu and Chiba regions in Kanto province, to construct database that can be applied in the future to provenance analysis of soil evidence from a crime scene. The sediments from the quaternary volcanic lithology of the Chiba region were found to be dominated by heavy minerals of volcanic origin - orthopyroxene, clinopyroxene, and amphibole, and the REEs (rare earth elements) within the region showed similar geochemical behavior. On the other hand, four distinct heavy mineral groups were identified in the sediments of the Kofu region, where there is a great variety of underlying bedrock, and the geochemical behavior of the REEs in the sediments also varied accordingly to their geological origins. As such, our study shows that high-resolution SR-XRD data can provide information on the spatial distribution patterns of heavy minerals in stream sediments, playing an important role in determining their likely geographical origin. Meanwhile, the highly sensitive HE-SR-XRF data allow us to study the geochemical behavior of trace heavy elements, especially the REEs in the sediments, providing additional support to further constrain the likely geographical origin of the sediments determined by heavy minerals.

Carbon-coated Na2FePO4F and Na2Fe0.5Mn0.5PO4F are successfully prepared by a simple solid-state method with ascorbic acid as carbon source. Crystal structure of Na2Fe0.5Mn0.5PO4F is found to be isostructural with Na2MnPO4F by an X-ray diffraction method, which has a three dimensional fluorophosphate framework. Scanning/transmission electron microscopy and Raman spectroscopy reveal that the addition of ascorbic acid effectively suppresses the particle growth of the samples, forming the nano-sized carbon coated materials. Electrode performance of Na2FePO4F is compared with that of Na2Fe0.5Mn0.5PO4F. The carbon-coated Na2FePO4F prepared with 2 wt% ascorbic acid delivers discharge capacity of 100–110 mAh g−1 at a rate of 1/20 C (6.2 mA g−1) with well-defined voltage plateaus at 3.06 and 2.91 V vs. Na metal. In contrast, Na2Fe0.5Mn0.5PO4F is less electrochemically active. The higher content of carbon by the adding ascorbic acid (6 wt%) and ball-milling treatment are necessary to achieve high reversible capacity. A well-optimized Na2Fe0.5Mn0.5PO4F sample delivers the discharge capacity of 110 mAh g−1 at a rate of 1/20 C (6.2 mA g−1), and it is first demonstrated that average operating voltage is higher than that of Na2FePO4F based on the possible Mn2+/Mn3+ redox couple centered at 3.53 V.

Carbon-coated Na2FePO4F is synthesized by a simple solid-state method with ascorbic acid as carbon source. Structural characterization of Na2FePO4F by synchrotron X-ray diffraction, scanning/transmission electron microscopy, and Raman spectroscopy reveals that ascorbic acid effectively suppresses the particle growth of Na2FePO4F, forming the nano-sized carbon coated materials. Electrode performance of Na2FePO4F for rechargeable sodium batteries is also examined. The carbon-coated Na2FePO4F sample (1.3 wt% carbon) delivers initial discharge capacity of 110 mAh g-1 at a rate of 1/20 C (6.2 mA g-1) with well-defined voltage plateaus at 3.06 and 2.91 V vs. Na metal. The sample also shows acceptable capacity retention and rate capability as the positive electrode materials for rechargeable Na batteries, which is operable at room temperature. Keywords: Na battery, Sodium insertion

Trees that accumulate metals are important plants for restoring contaminated soil because of their high biomass. We examined the cadmium (Cd) tolerance and growth rate of six willow (Salix) species common in Japan. To characterize in detail the localization of Cd and its ligands, synchrotron radiation-based micro X-ray fluorescence analysis was used. This revealed the accumulation of cadmium at the tips of the serrations in leaves, and the phellogen and/or the phelloderm under the stem surface. micro-X-ray absorption near edge structure spectra of Cd in all the accumulation sites were similar to that of the Cd ion coordinated by O ligands in S. gilgiana.

This paper reports on the distribution of Cd and essential elements in the stems of rice plants, 'Nipponbare' and 'Milyang 23', measured by synchrotron radiation micro-XRF imaging. X-ray absorption near edge structure (XANES) analysis was applied to estimate the chemical forms of Cd in the roots, stems and leaves, aiming to reveal the mechanisms of Cd transport in rice. The results show that the Cd concentration of 'Nipponbare' was found to be higher than that of 'Milyang 23' at the root, although there was no significant difference between these two cultivars at the shoot. In addition, the distribution of Cd and the essential elements inside the plant were clearly revealed by micro-XRF imaging. It was found that Cd was also localized to the bundle. The Cd K-edge XANES analysis indicated that Cd was bound to sulfur in the root for both rice plants. Furthermore, the content of Cd combining with S (Cd-S) in the stem of 'Nipponbare' became 1.5 times higher after exposing to Cd for a long time, while only a slight change in the stem of 'Milyang 23' was found. In contrast with the stem, the leaf of 'Nipponbare' contained a lower Cd-S content than that of the control after a long-term exposure, while that of 'Milyang 23' became higher. In conclusion, the difference in the chemical form of Cd at the shoots affected the different accumulation behaviors of Cd between 'Nipponbare' and 'Milyang 23'. (author)

実験室レベルで高感度な分析が可能な三次元偏光光学系蛍光X線分析装置を用いて，コーヒー豆の微量元素を定量し，統計解析を行った．産地判別に有用な元素を明らかにし，簡易・迅速な産地判別法として確立することを目指した．産地の指標となる6元素（Mn，Fe，Ni，Rb，Sr，Ba）を高感度に分析するために測定条件を最適化した結果，各元素において直線性のよい検量線を作成することができ，各元素の検出限界は，サブppmレベルとなった．コーヒー生豆75試料中の6元素を定量し，主成分分析を行った結果，6産地（ブラジル，コロンビア，ベトナム，インドネシア，タンザニア，グアテマラ）の生豆を特性化することができた．また，同ロットの生豆と焙煎豆の各元素濃度を比較した結果，これらの6元素について大きな差は見られなかったため，今回の産地判別手法における焙煎の影響は小さいことが分かった．本手法では，試料の前処理は10分程度，測定時間は2時間30分であり，自動連続測定が可能であることから，簡易・迅速な実用性の高い分析手法として，コーヒー豆の産地判別への応用が更に期待される．

犯罪捜査で重要な証拠物件となるポリエステル単繊維について，レーザーアブレーション（LA）－誘導結合プラズマ質量分析法（ICP-MS）によって検出された微量不純物を指標とした異同識別法の検討を行った．213 nmのNd : YAGレーザーを搭載したLA装置を最適化し，試料中にppmレベルで存在するCu，Sb，Baなどの微量元素を定量するための測定条件を検討した．自動車製造メーカー7社の23車種から得られたトランクマット単繊維31試料を試料として用いた．直径20 μm程度の単繊維試料について，Li，Mg，Al，P，Ca，Ti，Co，Cu，Ge，Nb，Sb，Pbの定量が可能であった．顕微FT-IRとSEM-EDSを用いる従来法と組み合わせると，31試料すべての識別が可能であった．このようにLA-ICP-MS法は，他のいかなる組成分析法より，試料前処理が迅速で極微小な試料の高感度分析が可能であった．本研究により，本法は自動車のトランクマットの単繊維の実用的な法科学分析法としてきわめて有用であることが初めて実証された．

Blue-painted pottery was produced in the New Kingdom, Egypt, and decorated with blue, red, and black pigment. In this study, two newly developed portable instruments, a portable X-ray fluorescence spectrometer and a portable X-ray powder diffractometer, were brought to the site on the outcrop at Northwest Saqqara, an archaeological site in Egypt, to verify their performance in on-site analysis of excavated artifacts at the site. Pigments used for the blue-painted pottery and plasters in the New Kingdom were analyzed by these instruments on the basis of both their chemical compositions and crystal-structural information. The blue pigments were identified as two different pigments, Egyptian blue and cobalt blue. The diffraction pattern of the blue pigment of the painted pottery exhibited that of spinel structure. The XRF spectrum of the blue pigment obtained by the same instrument from the same position indicates the presence of Mn, Co, Fe, Ni, and Zn. The possibility of compositional transitions of the cobalt blue pigment with time was revealed on by detailed analysis of the XRF data. The reason for the transitions is considered together with the archaeological background of the New Kingdom, Egypt.

To investigate the flow of the metal nutrients iron (Fe), zinc (Zn), manganese (Mn), and copper (Cu) during rice seed germination, we performed microarray analysis to examine the expression of genes involved in metal transport. Many kinds of metal transporter genes were strongly expressed and their expression levels changed during rice seed germination. We found that metal transporter genes such as ZIP family has tendency to decrease in their expressions during seed germination. Furthermore, imaging of the distribution of elements (Fe, Mn, Zn, and Cu) was carried out using Synchrotron-based X-ray microfluorescence at the Super Photon ring-8 GeV (SPring-8) facility. The change in the distribution of each element in the seeds following germination was observed by in vivo monitoring. Iron, Mn, Zn, and Cu accumulated in the endosperm and embryos of rice seeds, and their distribution changed during rice seed germination. The change in the patterns of mineral localization during germination was different among the elements observed.

小麦粉の産地判別を目的として，蛍光X線分析法により小麦粉中の微量元素の高感度定量を試みた．三次元偏光光学系エネルギー分散型蛍光X線分析装置を用い，測定条件を最適化した結果，小麦粉中の17元素（Na，Mg，Al，P，S，Cl，K，Ca，Mn，Fe，Cu，Zn，Br，Rb，Sr，Mo，Cd）において直線性のよい検量線を作成することができた．本法はサブppmレベルの重元素の定量が可能であった．63試料の小麦粉の定量分析を行ったところ，国産と外国産・混合とで微量元素組成に異なった傾向がみられた．更に，産地の指標となると考えられた特定の元素の定量値を用いた多変量解析から，国産の小麦粉をほぼ正確に判別できる判別式を構築することができた．本研究により，迅速・簡便な蛍光X線分析が産地判別に有用であることを示すことができた．今後は，本法がその他の食品へと応用されるだけでなく，多検体の分析を要する食品の品質検査における実用的な分析法として利用されることが期待される．

Potassic-ferropargasite, ideally KCa2(Fe42+Al)Si6Al2O22(OH)2, is a new member of the amphibole group occurring in a schistose calcareous hornfels from Kabutoichiba, Kameyama, Mie Prefecture, central Japan. The amphibole occurs as black subhedral to anhedral crystals, up to about 700 μm long, associated with calcite, biotite, K-feldspar, plagioclase, scapolite, chlorite and titanite. Potassic-ferropargasite is optically biaxial negative with α = 1.680(2), β = 1.690 (calc.), γ = 1.698(2) and 2V = 80-90°. The mineral is monoclinic, space group C2/m, with refined unit-cell parameters a = 9.937(5), b = 18.108(5), c = 5.335(4) A, β = 105.30(3)°, V = 926.0(9) A3, Z = 2. The three strongest lines in the X-ray powder-diffraction pattern [d in A (I) hkl] are 2.72 (100) 151, 8.48 (81) 110 and 2.61 (59) 061. Electron-microprobe gave SiO2 38.08, TiO2 1.92, Al2O3 15.12, Cr2O3 0.44, FeO 19.96, MnO 0.22, MgO 6.22, CaO 11.73, Na2O 1.57, K2O 2.74, F 0.13, Cl not detected, O = F + Cl -0.05, total 98.08 wt%, corresponding to (K0.54Na0.42)Σ0.96(Ca1.95Na0.05)Σ2.00(Fe2+2.59Mg1.44Al0.67Ti0.22Cr0.05Mn0.03)Σ5.00(Si5.91Al2.09)Σ8.00O22(OH1.94F0.06)Σ2.00 on the basis of O = 23, assuming OH + F + Cl = 2. The crystal structure of the clinoamphibole type was refined to an R of 6.5%.

高エネルギーX線を励起源とする3次元偏光光学系蛍光X線分析装置を用いて，犯罪に利用されることが多い布粘着テープの異同識別法の開発を試みた．検討の結果，識別に最適な分析条件は以下のとおりである．2次ターゲットとしてRhとAl2O3を用い，測定時間はそれぞれ300秒と600秒，分析に用いた元素はCa，Ti，Cr，Mn，Fe，Ni，Zn，Sr，Zr，Nb，Mo，Sb，Ba，Pbの14元素である．方法の有効性を検証するため，市販の布粘着テープ17社31試料へ応用した．糸密度と蛍光X線（XRF）スペクトルの14元素のピーク強度の組み合わせにより，31試料中29試料をうまく識別できることが分かった．識別できなかった2試料は同一起源のものと思われた．このように蛍光X線分析を用いる本方法は，非破壊で迅速，簡便であることから法科学的分析法として実用性が高いことが分かった．

Soil can be one of the most important physical evidence in a criminal investigation which contributes to prove a linkage between the suspect and the crime scene. In this work, the validity of multiple instrumental analytical techniques for forensic soil identification was studied using 148 soil samples collected from the Tokyo metropolitan area. The samples were characterized by X-ray diffraction (XRD) analysis, X-ray fluorescence (XRF) analysis, magnetic susceptibility determination, scanning electron microscopy with an energy dispersive X-ray spectrometer (SEM-EDS) and high-energy synchrotron radiation X-ray fluorescence (SR-XRF) analysis. It was found that soil samples collected from railway stations and roadside dust showed higher magnetic susceptibilities (≧0.5×10-4 m3 kg-1 for 25% of the samples collected ) than those of soil samples collected from rivers, ponds, and lakes (

野菜中の無機元素を簡便で高感度に定量するための蛍光X線分析法の開発を目的とした．その結果，三次元偏光光学系を採用したエネルギー分散型装置を用い，対象元素を高効率に励起できる二次ターゲットを選択し，発生する蛍光X線強度を散乱線で規格化することで野菜中のサブppm（μg g−1）レベルの重元素の分析が可能となった．本法を用いて群馬県産と岐阜県産のホウレンソウの分析を行ったところ，数% レベルの元素（K，Ca等）から数ppm程度の元素（Cd，Ba等）まで幅広い濃度範囲にわたる多元素を同時に定量できた．その結果，産地によりCa，Zn，Br，Rb，Mo，Ba等で含有量に違いが見られ，産地判別に応用できる可能性が示唆された．また，本法では，重元素の高感度分析が可能なことから，野菜中のCd含有量のスクリーニング検査としても有用であることが分かった．