Synchrotron X-ray Fluorescence Analysis Research Articles

Mechanistic analysis of the sub chronic toxicity of La and Gd in Daphnia magna based on TKTD modelling and synchrotron X-ray fluorescence imaging.

The release of lanthanides (Ln) into the environment has increased in recent decades due to their expanding applications in society. Studying their toxicity in aquatic ecosystems is urgent and challenging, with contradictory evidence presented in the literature. This study compared the biodistribution of La and Gd in Daphnia magna exposed to sub-chronic conditions and developed the first Toxicokinetic-Toxicodynamic (TKTD) model for these lanthanides with this model crustacean. D. magna were initially exposed for 7 days to concentrations close to the LC50 of La (2.10 mg L-1) and Gd (1.70 mg L−1). After exposure, half of the live daphnids were introduced in a clean media to allow depuration over 24 h, while the other organisms were directly prepared for synchrotron imaging measurements. Synchrotron X-ray fluorescence analysis revealed that metal distribution in the organisms was similar for both La and Gd, predominantly localized in the intestinal tract, even after the depuration process. These results indicate that ingested metal can adversely affect organisms under sub-chronic exposure conditions, highlighting the importance of using nominal concentrations as a more suitable indicator of metal bioavailability for risk assessment. The General Unified Threshold Model of Survival (GUTS) TKTD framework, in its reduced form (GUTS-RED), was developed for La and Gd using dissolved and nominal concentrations. D. magna were exposed for 7 days to concentrations from 0.5 to 5 mg L−1 of La or Gd and mortality monitored daily. The mechanistic model revealed a faster toxicokinetics for La than Gd and a higher toxicity for Gd than La in the organism. This study confirmed, despite similar chemical properties, the variation in both toxicity and toxicokinetics between these two metals.

Modulation of growth and chemical element accumulation in <i>Fragaria × ananassa</i> plants <i>in vivo</i> under the effect of silicon chelates

Due to the protective role played by silicon in plants against unfavorable environmental conditions, siliconcontaining preparations are of considerable interest as biostimulants. In this work, a mechanical composite of rice husk and green tea containing soluble silica chelate complexes was used as the source of silicon. The study aims to examine the effect of silicon chelates on the growth and physiological parameters and the chemical composition of Fragaria × ananassa plants (Solnechnaya Polyanka variety) under greenhouse conditions. The plants were watered using water without a mechanical composite (control) or an aqueous solution containing 0.3 g/L of mechanical composite twice per period. Sampling was carried out one week after the last treatment. In order to determine the concentration of chemical elements (Si, P, S, Cl, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, and Mo) in the roots and shoots of garden strawberry, it was proposed to use synchrotron X-ray fluorescence analysis. The use of the mechanical composite was shown to increase the amount of chlorophyll a, chlorophylls a and b, and carotenoids; decrease the amount of hydrogen peroxide; and increase the activity of the main antioxidant enzymes (superoxide dismutase, catalase, and peroxidase). It was determined that under the effect of the preparation, silicon accumulates primarily in shoots, affecting the accumulation of micro- and macroelements in the shoots and roots of plants. The obtained results substantiate the use of silicon-containing “green chemistry” as a means of controlling the growth and development of garden strawberry plants under in vivo conditions.

Combined Focused Ion Beam – Scanning Electron Microscope and Synchrotron X-ray Fluorescence analysis of multi-solid and melt inclusions from the super-giant Grasberg Cu[sbnd]Au deposit, Indonesia

Previous studies of the mineralised quartz veins from the Grasberg CuAu deposit in Indonesia have shown that they contain multi-solid inclusions and silicate melt inclusions. The multi-solid inclusions exhibit salinities up to 75 wt% NaCl equiv. and ultrahigh homogenisation (Vapour + Liquid + Solid → Liquid) temperatures, up to 1281 °C, but the processes leading to their formation are poorly understood. To determine the composition of these inclusions they were analysed by Focused Ion Beam – Scanning Electron Microscope (FIB-SEM) and Synchrotron X-ray Fluorescence (SXRF) techniques. FIB-SEM analysis of two representative multi-solid inclusions (MSI) showed that they contain a large halite and a smaller sylvite crystal and mixed KFe chloride crystals. K-feldspar crystals occurring inside and outside the multi-solid inclusions indicate that they were trapped from a melt phase. The ore-mineral chalcopyrite was also identified in one inclusion. Opening the multi-solid inclusions under vacuum resulted in a coating enriched in Na, K, Fe and Cl that precipitated on the crystals and walls of the inclusions. FIB-SEM analysis of a coexisting silicate melt inclusion showed that it consisted mainly of a devitrified glass with approximately K-feldspar composition that also contained small crystals of iron oxide. Further milling of the melt inclusion exposed a CuFe-rich silicate mineral. SXRF analysis of another multi-solid inclusion indicated that Br and Zn occur in the aqueous phase whereas K, Ca, Fe, Pb and Mn are hosted by solid phases within the inclusion.Modelling of mineralisation processes demonstrate that a supercritical, intermediate density fluid (with ~5 wt% NaCl) underwent an initial pressure drop causing phase separation and the formation of a vapour-rich fluid and a small fraction of brine, which led to the formation of salt hydrates, salt melts or both within the MSI. The coexistence of silicate melt inclusions and the occurrence of hematite and, K-feldspar in MSI suggest that a coeval silicate melt is also associated with mineralisation at the Grasberg deposit. The high salinity, multi-solid inclusions and melt inclusions form early in the vein paragenesis and record the origin and initial processes of ore deposition. Furthermore, the high metal-bearing capacity of salt melts suggests that the observation of coexisting silicate and salt melts may indicate the presence of a fertile mineral system.

Sr distribution as proxy for Ca distribution at depth in SXRF analysis of mm‐sized carbonaceous chondrites: Implications for asteroid sample return missions

AbstractReliable identification of chondrules, calcium‐aluminum‐rich inclusions (CAIs), carbonate grains, and Ca‐phosphate grains at depth within untouched, unprepared chondritic samples by a nondestructive analytical method, such as synchrotron X‐ray fluorescence (SXRF) computed tomography (CT), is an essential first step before intrusive analytical and sample preparation methods are performed. The detection of a local Ca‐enrichment could indicate the presence of such a component, all of which contain Ca as major element and/or Ca‐bearing minerals, allowing it to be precisely located at depth within a sample. However, the depth limitation from which Ca‐K fluorescence can travel through a chondrite sample (e.g., ∼115 µm through material of 1.5 g cm−3) to XRF detectors leaves many Ca‐bearing components undetected at deeper depths. In comparison, Sr‐K lines travel much greater distances (∼1700 µm) through the same sample density and are, thus, detected from much greater depths. Here, we demonstrate a clear, positive, and preferential correlation between Ca and Sr and conclude that Sr‐detection can be used as proxy for the presence of Ca (and, thus, Ca‐bearing components) throughout mm‐sized samples of carbonaceous chondritic material. This has valuable implications, especially for sample return missions from carbonaceous C‐type asteroids, such as Ryugu or Bennu. Reliable localization, identification, and targeted analysis by SXRF of Ca‐bearing chondrules, CAIs, and carbonates at depth within untouched, unprepared samples in the initial stages of a multianalysis investigation insures the valuable information they hold of pre‐ and post‐accretion processes in the early solar system is neither corrupted nor destroyed in subsequent processing and analyses.

Trace elemental behavior in the solar nebula: Synchrotron X-ray fluorescence analyses of CM and CR chondritic iron sulfides and associated metal

We have performed a coordinated focused ion beam (FIB)-scanning and transmission electron microscopy (SEM, TEM)-electron probe microanalysis (EMPA)-synchrotron X-ray fluorescence (SXRF) microprobe study to determine phase-specific microstructural characteristics and high-resolution in situ trace element concentrations of primary pyrrhotite, pentlandite, and associated metal grains from chondrules in CM2 and CR2 carbonaceous chondrites. This work is the first of its kind to link trace element chemical and microstructural observations in chondritic sulfides in an attempt to determine formation mechanisms and conditions of primary sulfides in these meteorite groups. SXRF and TEM analyses were performed on a small number of FIB sections which act as representative samples of primary sulfides and associated metal present in pyrrhotite-pentlandite intergrowth (PPI) grains and sulfide-rimmed metal (SRM) grains.SXRF microprobe analyses allowed the concentrations of the minor and trace elements, Co, Cu, Ge, Zn, and Se to be quantified, in addition to Fe and Ni, at a spatial resolution of 2 µm. The similarity between the CM and CR PPI sulfide trace element patterns provides evidence for a common formation mechanism for this type of sulfide grain in both meteorite groups. In addition, the SRM sulfide and metal have comparable trace element patterns that indicate a genetic relationship between the two, such as sulfidization of metal. Enrichments in Ni, Co, Cu, and Se are consistent with the chalcophile/siderophile behavior of these elements. The observed depletions in Ge suggest that it may have been lost by evaporation or else was never incorporated into the metal or sulfide precursor materials. The depletion in Zn may also be attributable to evaporation, but, being partially lithophile, may also have been preferentially incorporated into silicates during chondrule formation. Trace element concentrations support crystallization from an immiscible sulfide melt in chondrules for formation of the PPI grains and sulfidization of metal for the origin of the SRM grains.

Effects of arsenic on the distribution and mode of occurrence of gold during fluid-pyrite interaction: A case study of pyrite from the Qiucun gold deposit, China

Abstract This paper presents the results of an investigation of the incorporation of Au within pyritic ore from the Qiucun epithermal Au deposit, China. The new data provide insights into the mode of occurrence of Au during fluid-rock interactions within epithermal systems. The distribution and mode of occurrence of Au within arsenian pyrite were investigated using a chemical and structural characterization-based approach combining laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) trace element analysis, megapixel synchrotron X-ray fluorescence analysis (MSXRF), and atom probe tomography (APT). The resulting data indicate that invisible Au is present at elevated concentrations in the form of a homogeneous solid solution within As-rich pyrite domains, which yields Au concentrations that positively correlate with As. Arsenic-induced lattice defects, such as stacking faults and the expansion of the pyrite unit cell, provide evidence of the effect of As on the incorporation of Au into pyrite. The nucleation and crystallization of electrum preferentially occurred at the fluid-pyrite reaction interface or along fractures and grain boundaries within the pre-existing pyrite. This study indicates that changes in physicochemical conditions (e.g., temperature, pH, and sulfur fugacity) during fluid-pyrite interactions are key controls on the development of nanometer- or micrometer-scale clusters of gold. The systematic compositional and textural observations documented in this study provide new insights into the mechanisms responsible for the different modes of occurrence of Au (ionic vs. particulate) and enable us to further understand the processes involved in the formation of Au mineralization.

Synchrotron-based X-ray fluorescence study of gold nanorods and skin elements distribution into excised human skin layers.

Understanding the distribution of nanoparticles in skin layers is fundamentally important and essential for developing nanoparticle-based dermal drug delivery systems. In the present study, we provide insights into the distribution of gold nanorods (GNRs) functionalized with hydrophobic or hydrophilic ligands in human skin layers using synchrotron X-ray fluorescence (SR-XRF) spectroscopy, confocal microscopy, and transmission electron microscopy. The results confirmed the important role that the surface chemistry of GNRs plays in their penetration into the skin; the GNRs coated with polyethylene glycol were distributed into the skin layers to a greater extent than the GNRs coated with hydrophobic polystyrene thiol. In addition, SR-XRF analysis revealed that the spatial distribution of endogenous elements (phosphorus and sulfur) in skin layers demonstrated a significant "anti-correlation" relationship with that of GNRs. These results suggest possible association (via adsorption) between the GNRs and these two elements localized in skin, which can be valuable for understanding the penetration mechanism of gold nanoparticles into the skin.

Recombination of Correlations between Bioelements in the Liver and Lungs during Modeling of Diet-Induced Obesity.

In rats with obesity induced by high fat ration, the concentrations of K, Ca, Mn, Fe, Cu, Zn, Se, Br, Rb, and Sr were measured in the liver and lungs using synchrotron X-ray fluorescence analysis. Recombinations of inter-element correlations in the liver and lungs of rats receiving or not receiving additional Zn were observed under fasting conditions and after eating lard. Sr and Ca made the most pronounced contribution in the redistribution of correlations in the liver of obese rats. In contrast to other bioelements, Sr had negative correlations with all study elements in the liver of obese rats during physiological starvation. Long-term administration of Zn to rats was followed by recombination of both fasting and postprandial inert-element correlations in the liver and lungs, but Zn concentration did not change under these conditions. Redistribution of correlations in the liver and lungs of obese rats under fasting conditions reflects fundamental changes in metabolic processes, while redistribution observed after fat meal indicates temporary (postprandial) changes.

シンクロトロン蛍光X線分析法による世界文化遺産三重津海軍所跡（佐賀市）出土磁器の胎土分析 ─第1報，陶石，佐賀城跡出土磁器との比較─

A lot of porcelains were found at the Mietsu Naval Facility Site in Saga, Japan, which was approved as a World Heritage by UNESCO in July, 2015. We determined the X-ray fluorescence intensity ratios of Fe, Rb, Sr, Y and Zr involved in the body clay of the porcelains by synchrotron X-ray fluorescence analysis, and compared them with those excavated from the Saga castle site and with Amakusa or Izumiyama porcelain stones. The X-ray fluorescence intensity ratio of each element was the highest for Fe in all samples, but other chemical elements depended on the kind of porcelain and the porcelain stone. Sr was the lowest for porcelain stones, but increased greatly for porcelains. A plot of log {Intensity ratio (Rb/Sr)} vs. log {Intensity ratio (Zr/Sr)} gave a good straight line. The data for the porcelain stones gathered in the 1st quadrant and those of the porcelains of the Saga castle site shifted a little to the left lower side, but those of porcelains of the Mietsu Naval Facility site shifted to the more left and lower side. The change in the intensity ratio of elements was ascribed to the porcelain stones used and to the manufacturing process of the clay.

Monochromatic computed microtomography using laboratory and synchrotron sources and X-ray fluorescence analysis for comprehensive analysis of structural changes in bones.

A combination of X-ray tomography at different wavelengths and X-ray fluorescence analysis was applied in the study of two types of bone tissue changes: prolonged presence in microgravity conditions and age-related bone growth. The proximal tail vertebrae of geckos were selected for investigation because they do not bear the supporting load in locomotion, which allows them to be considered as an independent indicator of gravitational influence. For the vertebrae of geckos no significant differences were revealed in the elemental composition of the flight samples and the synchronous control samples. In addition, the gecko bone tissue samples from the jaw apparatus, spine and shoulder girdle were measured. The dynamics of structural changes in the bone tissue growth was studied using samples of a human fetal hand. The hands of human fetuses of 11-15 weeks were studied. Autonomous zones of calcium accumulation were found not only in individual fingers but in each of the investigated phalanges. The results obtained are discussed.

Understanding metal homeostasis in primary cultured neurons. Studies using single neuron subcellular and quantitative metallomics.

The purpose of this study was to demonstrate how single cell quantitative and subcellular metallomics inform us about both the spatial distribution and cellular mechanisms of metal buffering and homeostasis in primary cultured neurons from embryonic rat brain, which are often used as models of human disease involving metal dyshomeostasis. The present studies utilized synchrotron radiation X-ray fluorescence (SRXRF) and focused primarily on zinc and iron, two abundant metals in neurons that have been implicated in the pathogenesis of neurodegenerative diseases such as Alzheimer's disease and Parkinson's disease. Total single cell contents for calcium, iron, zinc, copper, manganese, and nickel were determined. Resting steady state zinc showed a diffuse distribution in both soma and processes, best defined by the mass profile of the neuron with an enrichment in the nucleus compared with the cytoplasm. Zinc buffering and homeostasis was studied using two modes of cellular zinc loading - transporter and ionophore (pyrithione) mediated. Single neuron zinc contents were shown to statistically significantly increase by either loading method - ionophore: 160 million to 7 billion; transporter 160 million to 280 million atoms per neuronal soma. The newly acquired and buffered zinc still showed a diffuse distribution. Soma and processes have about equal abilities to take up zinc via transporter mediated pathways. Copper levels are distributed diffusely as well, but are relatively higher in the processes relative to zinc levels. Prior studies have observed iron puncta in certain cell types, but others have not. In the present study, iron puncta were characterized in several primary neuronal types. The results show that iron puncta could be found in all neuronal types studied and can account for up to 50% of the total steady state content of iron in neuronal soma. Although other metals can be present in iron puncta, they are predominantly iron containing and do not appear to be associated with ferritin cages or transferrin receptor endosomes. The iron content and its distribution in puncta were similar in all neuron types studied including primary dopaminergic neurons. In summary, quantitative measurements of steady state metal levels in single primary cultured neurons made possible by SRXRF analyses provide unique information on the relative levels of each metal in neuronal soma and processes, subcellular location of zinc loads, and have confirmed and extended the characterization of heretofore poorly understood cytoplasmic iron puncta.

Study of the distribution of elements between a cyanobacterial community and a carbonate body of a hot spring via synchrotron XRF analysis

The contents of many elements in a microbial community and various associations of a carbonate body from the Garga hot spring (Barguzin Valley, Baikal Rift Zone) were analyzed with a synchrotron X-ray fluorescence analysis. The coefficients of biological accumulation have been determined. The contents of practically all elements, except for Sr, in the microbial community are higher than in the carbonate body, and the Ge and Zn contents are higher by an 2 order of magnitude. The vertical cross section of the carbonate body contains three associations two of which formed as a result of microbial activity. The contents of elements in all associations are similar. The Ge content in the microbial community is 270 ppm, on average, whereas in the carbonate body it is less than 2 ppm. The elevated Ge contents could serve as a diagnostic indicator of the microbial community’s development around the sulfide-less alkaline hot springs in the presence of increased contents of radium isotopes. A sample of the carbonate body with layers formed as a result of the microbial community activity was continuously scanned with a step of 0.5 mm. No Ge-rich areas were determined, which indicates its removal by solutions during the destruction of organic matter.

Development of heavy mineral and heavy element database of soil sediments in Japan using synchrotron radiation X-ray powder diffraction and high-energy (116keV) X-ray fluorescence analysis

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.

A comparison of biogenic iron quotas during a diatom spring bloom using multiple approaches

Abstract. Biogenic Fe quotas were determined using three distinct techniques on samples collected concurrently in the subtropical Pacific Ocean east of New Zealand. Fe quotas were measured using radioisotope uptake experiments (24 h incubation), bulk filtration and analysis by inductively-coupled plasma mass spectrometer (ICPMS), and single-cell synchrotron x-ray fluorescence (SXRF) analysis over a sixteen-day period (year days 263 to 278 of 2008) during a quasi-Lagrangian drifter experiment that tracked the evolution of the annual spring diatom bloom within a counter-clockwise open-ocean eddy. Overall, radioisotope uptake-determined Fe quotas (washed with oxalate reagent to remove extracellular Fe) were the lowest (0.5–1.0 mmol Fe:mol P; 4–8 μmol Fe:mol C), followed by single-cell Fe quotas (2.3–7.5 mmol Fe:mol P; 17–57 μmol Fe:mol C), and the highest and most variable quotas were from the bulk filtration ICPMS approach that used the oxalate reagent wash, corrected for lithogenic Fe using Al (0.8–21 mmol Fe:mol P; 4–136 μmol Fe:mol C). During the evolution of the spring bloom within the eddy (year days 263 to 272), the surface mixed layer inventories of particulate biogenic elements (C, N, P, Si) and chlorophyll increased while Fe quotas estimated from all three approaches exhibited a general decline. After the onset of the bloom decline, the drogued buoys exited the eddy center (days 273 to 277). Fe quotas returned to pre-bloom values during this part of the study. Our standardized and coordinated sampling protocols reveal the general observed trend in Fe quotas: ICPMS > SXRF > radioisotope uptake. We discuss the inherent differences between the techniques and argue that each technique has its individual merits and uniquely contributes to the characterization of the oceanic particulate Fe pool.

Five hundred years of mercury exposure and adaptation.

Mercury is added to the biosphere by anthropogenic activities raising the question of whether changes in the human chromatin, induced by mercury, in a parental generation could allow adaptation of their descendants to mercury. We review the history of Andean mining since pre-Hispanic times in Huancavelica, Peru. Despite the persistent degradation of the biosphere today, no overt signs of mercury toxicity could be discerned in present day inhabitants. However, mercury is especially toxic to the autonomic nervous system (ANS). We, therefore, tested ANS function and biologic rhythms, under the control of the ANS, in 5 Huancavelicans and examined the metal content in their hair. Mercury levels varied from none to 1.014 ppm, significantly less than accepted standards. This was confirmed by microfocused synchrotron X-ray fluorescence analysis. Biologic rhythms were abnormal and hair growth rate per year, also under ANS control, was reduced (P < 0.001). Thus, evidence of mercury's toxicity in ANS function was found without other signs of intoxication. Our findings are consistent with the hypothesis of partial transgenerational inheritance of tolerance to mercury in Huancavelica, Peru. This would generally benefit survival in the Anthropocene, the man-made world, we now live in.

Concentration of various trace elements in the rat retina and their distribution in different structures

Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify the total amount of trace elements in retina from adult male Sprague-Dawley rats (n = 6). Concentration of trace elements within individual retinal areas in frozen sections of the fellow eye was established with the use of two methodologies: (1) particle-induced X-ray emission (PIXE) in combination with 3D depth profiling with Rutherford backscattering spectrometry (RBS) and (2) synchrotron X-ray fluorescence (SXRF) microscopy. The most abundant metal in the retina was zinc, followed by iron and copper. Nickel, manganese, chromium, cobalt, selenium and cadmium were present in very small amounts. The PIXE and SXRF analysis yielded a non-homogenous pattern distribution of metals in the retina. Relatively high levels of zinc were found in the inner part of the photoreceptor inner segments (RIS)/outer limiting membrane (OLM), inner nuclear layer and plexiform layers. Iron was found to accumulate in the retinal pigment epithelium/choroid layer and RIS/OLM. Copper in turn, was localised primarily in the RIS/OLM and plexiform layers. The trace elements iron, copper, and zinc exist in different amounts and locations in the rat retina.

Synchrotron X-ray fluorescence analysis in environmental and earth sciences

Compared to other microscopic analytical tools X-ray microscopy techniques have the advantage that the large penetration depth of X-rays in matter allows one to investigate the interior of an object without destructive sample preparation. In combination with X-ray fluorescence tomography, analytical information from inside of a specimen can be obtained. Different X-ray analytical techniques can be used to produce contrast, X-ray absorption, fluorescence, and diffraction, to yield chemical, elemental, and structural information about the sample. Scanning microscopy on the basis of various lens systems in synchrotron radiation sources provides a routine spatial resolution of now about 100 nanometer but in the foreseeable future a 10–20 nanometer spatial resolution can be expected. X-ray absorption spectrometry can also provide chemical (speciation) information on the sample. All this makes X-ray microscopy attractive to many fields of science. In this paper the techniques are briefly reviewed and a number of applications in the earth, planetary and cosmos sciences are illustrated with state-of-the art examples, while applications in the environmental sciences and biology are also briefly discussed.

NanoSIMS analysis of arsenic and selenium in cereal grain

*Cereals are an important source of selenium (Se) to humans and many people have inadequate intakes of this essential trace element. Conversely, arsenic (As) is toxic and may accumulate in rice grain at levels that pose a health risk. Knowledge of the localization of selenium and arsenic within the cereal grain will aid understanding of their deposition patterns and the impact of processes such as milling. *High-resolution secondary ion mass spectrometry (NanoSIMS) was used to determine the localization of Se in wheat (Triticum aestivum) and As in rice (Oryza sativa). Combined synchrotron X-ray fluorescence (S-XRF) and NanoSIMS analysis utilized the strengths of both techniques. *Selenium was concentrated in the protein surrounding the starch granules in the starchy endosperm cells and more homogeneously distributed in the aleurone cells but with Se-rich hotspots. Arsenic was concentrated in the subaleurone endosperm cells in association with the protein matrix rather than in the aleurone cells. NanoSIMS indicated that the high intensity of As identified in the S-XRF image was localized in micron-sized hotspots near the ovular vascular trace and nucellar projection. *This is the first study showing subcellular localization in grain samples containing parts per million concentrations of Se and As. There is good quantitative agreement between NanoSIMS and S-XRF.

Do acupuncture points exist?

We used synchrotron x-ray fluorescence analysis to probe the distribution of four chemical elements in and around acupuncture points, two located in the forearm and two in the lower leg. Three of the four acupuncture points showed significantly elevated concentrations of elements Ca, Fe, Cu and Zn in relation to levels in the surrounding tissue, with similar elevation ratios for Cu and Fe. The mapped distribution of these elements implies that each acupuncture point seems to be elliptical with the long axis along the meridian.

Evolution of the oxide structure of 9CrODS steel exposed to supercritical water

The corrosion behavior and oxide structure of 9CrODS steel in supercritical water has been studied. Samples were exposed to supercritical water at 500 and 600 °C for times of 2, 4 and 6 weeks. The oxide structure was studied using microbeam synchrotron X-ray diffraction and fluorescence analysis. The 600 °C samples exhibited a three-layer structure with Fe 3O 4 in the outer layer, a mixture of FeCr 2O 4 and Fe 3O 4 in the inner layer, and a mixture of metal and oxide grains (FeCr 2O 4 and Cr 2O 3) in the diffusion layer. Between the 2 and 4-week samples exposed to 600 °C supercritical water, a Cr 2O 3 film appeared at the diffusion layer–metal interface which appears to be associated with slower oxidation of the metal. The 500 °C samples also showed a three-layer structure, but both the outer and inner oxide layers contained mainly Fe 3O 4, and the diffusion layer contained much fewer oxide precipitates and was a solid solution of oxygen ahead of the oxide front.