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Studying climate changes in the Eastern Mediterranean and Aegean region, particularly in Western Anatolia, is crucial for understanding environmental dynamics over time. We present high‐resolution, long‐term micro‐X‐ray fluorescence data from Buldan Yayla Lake (Denizli‐Buldan), a key area, covering the period from the Last Glacial Maximum (LGM) to the present. Sedimentological and paleoclimate data are supported by high‐resolution radiocarbon analyses, as well as two tephra chronologies from Cape Riva and Minoan. According to the results, a cold and arid climate is observed during the LGM, Post‐LGM and Younger Dryas. From the LGM to the present, there has been a trend towards increasing warmth and humidity. During the Late Glacial (LG) and Holocene (especially in the early Holocene), the climate was warmer and more humid. A short‐lived climate change associated with the Older Dryas is recorded during the Bølling–Allerød warm period (~13 200–12 350 cal a bp) within the LG. The data indicate that the sediment cores of Buldan Yayla Lake are highly sensitive in reflecting climate information between the LGM and the present day. At the same time, the climate in Western Anatolia is recorded as more stable throughout the Holocene. In conclusion, this study enhances our understanding of Western Anatolia's climate dynamics and environment–society relationship from the LGM to the present. [ABSTRACT FROM AUTHOR]

The scientific characterization of historical pieces reflects the history of a people, as it brings countless information about the technology and cultural knowledge of a given civilization. These studies often involve a certain level of interdisciplinarity, as technology and history come together in the search for the characterization of a piece. In many cases it is possible to determine the period in which the artifact was created, identify the techniques used by the artist, provide data of a possible restoration process, in addition to helping to identify possible forgeries in valuable works. In this paper, two non-destructive characterization techniques were used: micro-X-ray fluorescence (µXRF) and X-ray microtomography (µCT), with the aim of characterizing a wooden Our Lady of the Immaculate Conception sculpture. µXRF measurements were carried out at 30 spots on the sculpture to identify the pigments used. It was possible to detect overlapping layers of paint, the presence of gold in some ornaments, and the use of pigments that have not been used since the 19th century, such as vermilion. The images generated by µCT were used to analyze the internal structure of the piece, its fixing points and the techniques used by the artist, in addition to enabling the observation of hollow. From the results obtained, it is concluded that two types of wood were used, the vermilion pigment applied in the mouth area is likely original, and the piece has probably undergone restoration.

The anisotropic textures, including unidirectional solidification textures and graphic intergrowths, characteristic for pegmatites, are interpreted to result from disequilibrium crystallization at high degrees of undercooling. Experimental studies have revealed the existence of thin boundary layers surrounding the rapidly growing crystals. Here, tourmaline-bearing samples from the outer zones of the Emmons pegmatite (Maine, U.S.A.) are used to examine if a boundary layer can also occur in natural samples. Crystal morphology is linked with geochemistry to understand the evolution of pegmatite melts and to constrain disequilibrium conditions at large degrees of undercooling. Petrographic studies and semiquantitative micro-X-ray fluorescence element mapping were conducted to identify crystal morphology and zonation, complemented with electron microprobe analyses to determine major and minor element compositions and LA-ICP-MS analyses of selected trace elements. Three textural groups were identified: comb-like tourmaline, quartz-tourmaline intergrowths, and radiating tourmaline. The intergrowths are optically coherent and are split into three different morphologies: central, second tier, and skeletal tourmaline. Most tourmaline is schorl, but chemical variation occurs on three different scales: between textural groups, between different morphologies, and intracrystalline. The largest scale geochemical variation is caused by the progressive evolution of the melt as it crystallized from the borders inwards, while the intracrystalline variations are attributed to sector zoning. A model is suggested where the systematic variation of Mg, Mn, and Fe within individual intergrowths is proposed to be the result of crystallization from a boundary layer, rich in water and other fluxing elements (e.g., Li, P, B), formed around the rapidly growing central tourmaline. Here, we show the first examples of boundary layers in natural pegmatites. Furthermore, the results bring into question whether boundary layer tourmaline can be used as a bulk melt indicator in pegmatitic melts. [ABSTRACT FROM AUTHOR]

Abstract Background The increase in the frequency and intensity of droughts is pointed out as one of the main factors altering biogeochemical cycles in the Amazon basin. An eco-nutritional approach using X-ray fluorescence micro-analysis (µXRF) is proposed to verify the long- and short-term effects of droughts on the growth and xylem nutrient concentrations of Cedrela fissilis Vell. Methods Fourteen radii were selected from a tree-ring width chronology and X-rayed by Itrax Multiscanner. Profiles of ring width, wood density, and concentrations of aluminum (Al), phosphorus (P), sulfur (S), calcium (Ca), potassium (K), manganese (Mn), iron (Fe) and strontium (Sr) together with Al/Ca, Ca/Mn, K/Ca, Sr/Ca and Mn/S ratios were constructed and correlated with precipitation, temperature, the difference between precipitation and potential evapotranspiration (P-PET) and standardized precipitation–evapotranspiration index (SPEI). Results During dry years, C. fissilis showed narrower, less dense rings, lower Al, P, S and Ca, and higher K and Fe concentrations (the opposite was found in wet years). Ring width decreased (together with Al, P, S, K, Ca, Mn, Fe, Sr, Al/Ca, K/Ca and Sr/Ca) and wood density increased (together with Ca/Mn and Mn/S), which was associated with an increase in evapotranspiration and temperature over time, mainly since 1990. Cedrela fissilis showed a tendency to increase its capacity for resistance, and a recovery and resilience in growth over time associated with responses in Al, Ca, P and S. However, it showed a risk in the capacity for recovery of the pre-drought density values, associated with unsatisfactory responses in Al, Ca, K, Fe and P. Conclusions This study is the first attempt to analyze tree-ring nutritional evidences of C. fissilis trees to climate sensitivity and resilience to drought, based on long-term data from seasonal moist tropical forests of the Amazon. Our data suggested that C. fissilis is undergoing alterations in the concentration, use and redistribution of nutrients associated with increasing wood density and decreasing growth over time, due to the increase of drought frequency in the southern Amazon.

Sediment geochemistry is one lens through which lake sediments are studied to reconstruct local and regional environmental processes. The measurement of sediment elemental composition has historically relied on expensive and destructive methods that limit the spatial and temporal scale of study. Micro-X-ray fluorescence (µXRF) core scanning offers a non-destructive, high-resolution alternative, but its results (i.e., intensity expressed as counts per second) are considered semi-quantitative and comparison among sites requires calibration. Calibration methods are emerging, although they are not yet widely employed and require further assessment of their efficacy. Using 135 sediment samples from 48 lakes across Canada, we assessed the congruence between µXRF and conventionally measured element compositions with various normalization and calibration techniques. Normalization of µXRF data to common proxies (e.g., Ca, Si, Ti, coherence:incoherence ratio, and total counts per second) often improved correlations between µXRF and conventional data, but increases were modest and not consistent for all elements. Our results suggest that µXRF normalization techniques should be applied cautiously, as no proxy represents a “one-size-fits-all” solution. The performance of multivariate log-ratio calibration (MLC) was more consistent, yielding moderate to strong improvement of the correlations between reference and predicted element concentrations. Random forest regression models outperformed partial least squares regression models for almost all elements. MLC may be applied where knowledge of elemental concentration is of great importance, or when comparing across multiple sites with diverse sediment geochemistries. Overall, our results reinforce uncalibrated µXRF core scanning as a strong investigative tool for measuring sediment geochemistry. Although calibrated µXRF data shows promise, conventional methods for measuring sediment geochemistry are still necessary for comparing element concentrations with sediment quality guidelines.

Background: The increase in the frequency and intensity of droughts is pointed out as one of the main factors altering biogeochemical cycles in the Amazon basin. An eco-nutritional approach using X-ray fluorescence micro-analysis (µXRF) is proposed to verify the long- and short-term effects of droughts on the growth and xylem nutrient concentrations of Cedrela fissilis Vell. Methods: Fourteen radii were selected from a tree-ring width chronology and X-rayed by Itrax Multiscanner. Profiles of ring width, wood density, and concentrations of aluminum (Al), phosphorus (P), sulfur (S), calcium (Ca), potassium (K), manganese (Mn), iron (Fe) and strontium (Sr) together with Al/Ca, Ca/Mn, K/Ca, Sr/Ca and Mn/S ratios were constructed and correlated with precipitation, temperature, the difference between precipitation and potential evapotranspiration (P-PET) and standardized precipitation–evapotranspiration index (SPEI). Results: During dry years, C. fissilis showed narrower, less dense rings, lower Al, P, S and Ca, and higher K and Fe concentrations (the opposite was found in wet years). Ring width decreased (together with Al, P, S, K, Ca, Mn, Fe, Sr, Al/Ca, K/Ca and Sr/Ca) and wood density increased (together with Ca/Mn and Mn/S), which was associated with an increase in evapotranspiration and temperature over time, mainly since 1990. Cedrela fissilis showed a tendency to increase its capacity for resistance, and a recovery and resilience in growth over time associated with responses in Al, Ca, P and S. However, it showed a risk in the capacity for recovery of the pre-drought density values, associated with unsatisfactory responses in Al, Ca, K, Fe and P. Conclusions: This study is the first attempt to analyze tree-ring nutritional evidences of C. fissilis trees to climate sensitivity and resilience to drought, based on long-term data from seasonal moist tropical forests of the Amazon. Our data suggested that C. fissilis is undergoing alterations in the concentration, use and redistribution of nutrients associated with increasing wood density and decreasing growth over time, due to the increase of drought frequency in the southern Amazon. [ABSTRACT FROM AUTHOR]

Norilsk sulfide ores are one of the largest known sources of Pd on Earth. Palladium in these ores is presented in platinum-group minerals (PGM) and base metal sulfides (BMS), especially in pentlandite [(Fe,Ni)9S8]. Although several studies demonstrated high concentrations along with heterogeneous distribution of Pd in pentlandites from Norilsk, the form of Pd in pentlandite has not been established. Here, we provide the first evidence for Pd incorporation in the structure of pentlandite from Norilsk ores using X-ray absorption near edge structure (XANES) spectroscopy, synchrotron-based micro-X-ray fluorescence (μXRF), and electron backscatter diffraction (EBSD). We present the first ever measured XANES spectra of Pd in pentlandite and atokite [(Pd,Pt)3Sn] as well as in other common Pd minerals. Divalent Pd in pentlandite was detected by XANES. The Pd spectra in pentlandite show no similarities with Pd spectra in PGM, metallic Pd, PdS, PdCl2, and PdSO4 which signifies that Pd incorporates into the lattice of pentlandite. Substitution of Ni by Pd in the lattice of pentlandite is supported by negative correlations shown by μXRF and electron probe microanalysis (EPMA) and complies with the previous studies. The additional EBSD study demonstrates a resemblance in cell parameters of the Pd-rich and Pd-poor parts of the pentlandite grains and reflects that Pd incorporation into the pentlandite structure does not imply any notable structure distortion. The combination of analytical techniques used in the present study demonstrates the great potential of these methods for understanding the mechanisms of noble metal incorporation into ore minerals. [ABSTRACT FROM AUTHOR]

In this study, the assessment of uncertainties introduced at different stages of the elemental analysis of archaeological ceramics has been described using the example of the Neolithic pottery sherds from Popovsky Lug (eastern Siberia). To evaluate the uncertainty introduced by sampling due to ceramic heterogeneity, three original sherds were cut into small subsamples. Powdered subsamples (250–350 mg) were analyzed using wavelength-dispersive X-ray fluorescence and inductively coupled plasma mass spectrometry methods, and the variations between analytical results for independent subsamples were compared with the variations introduced during the analytical process (measurement and sample preparation). It was shown that 250–350 mg of ceramic is sufficient to obtain good reproducibility (2–15%) between separate subsamples for most major and trace elements, even for the heterogeneous Neolithic ceramics included in this study. The differing behavior of concentration variations in some elements was explained by measuring the ceramic cross-sections by scanning electron microscopy and micro-X-ray fluorescence spectrometry, as well as by the theoretic modeling of the sampling error. The described workflow can be useful in finding uncertainties in elemental analysis results, which may affect the interpretation of bulk chemical composition in ceramic provenance studies.

The scientific examination and comparative investigation of pigments are fundamental for further understanding and analysis of historic and artistic works, and particularly useful for conservators. In fine art authentication, investigations are strongly focused on the identification of the painting materials used by the author. This study is focused on the use of non-invasive analytical techniques to increase the knowledge of the painting technique of Olga Boznańska. The aim of this study was to assess the technology, painting technique, and materials used by Olga Boznańska. The pallets, tubes with the paints, and several oil paintings were studied. For each painting, a series of images were recorded using various ranges of electromagnetic radiation, including near-infrared, visible light, ultraviolet, and X-rays. In order to characterize the pigments present in the paint layer, measurements of the elemental composition by X-ray fluorescence spectroscopy (XRF) were carried out. The ground layers and paints were measured with infrared spectroscopy (FTIR). This allowed us to identify the artist’s painting technique and determine how she executed her painting, how she applied the paints, and what pigments she used.

Die heterogene lichtgetriebene Katalyse ist ein Eckpfeiler nachhaltiger Energieumwandlung. Die meisten katalytischen Studien konzentrieren sich auf die Analyse von Wasserstoff und Sauerstoff, wobei in der Regel über die Gesamtantwort gemittelt wird, und somit eine Korrelation von Heterogenitäten der Matrix mit unterschiedlichen molekularen Aktivitäten limitiert ist. Hier berichten wir von Untersuchungen eines heterogenisierten Katalysator‐Photosensibilisator‐Systems, bei dem ein Polyoxometalat‐Katalysator zur Wasseroxidation und ein molekularer Modell‐Photosensibilisator gemeinsam in einer nanoporösen Blockcopolymer‐Membran immobilisiert wurden. Mittels elektrochemischer Rastersondenmikroskopie (SECM) wurde die lichtinduzierte Sauerstoffentwicklung mit Natriumperoxodisulfat (Na2S2O8) als Opferelektronenakzeptor an den modifizierten Blockcopolymer‐Membranen lokal bestimmt. Ex situ elementspezifische Analysen erzielten räumlich Informationen über die lokale Konzentration und Verteilung der molekularen Komponenten. Untersuchungen der modifizierten Membranen mittels abgeschwächter Infrarot‐Totalreflexion (IR‐ATR) zeigten keinen Abbau des Wasseroxidationskatalysators unter den beschriebenen lichtinduzierten Bedingungen. [ABSTRACT FROM AUTHOR]

Heterogeneous light‐driven catalysis is a cornerstone of sustainable energy conversion. Most catalytic studies focus on bulk analyses of the hydrogen and oxygen evolved, which impede the correlation of matrix heterogeneities, molecular features, and bulk reactivity. Here, we report studies of a heterogenized catalyst/photosensitizer system using a polyoxometalate water oxidation catalyst and a model, molecular photosensitizer that were co‐immobilized within a nanoporous block copolymer membrane. Via operando scanning electrochemical microscopy (SECM), light‐induced oxygen evolution was determined using sodium peroxodisulfate (Na2S2O8) as sacrificial electron acceptor. Ex situ element analyses provided spatially resolved information on the local concentration and distribution of the molecular components. Infrared attenuated total reflection (IR‐ATR) studies of the modified membranes showed no degradation of the water oxidation catalyst under the reported light‐driven conditions. [ABSTRACT FROM AUTHOR]

PolyX is a compact bending magnet beamline under construction at National Synchrotron Radiation Centre SOLARIS, which will be available to users in mid-2023. The beamline is focused on X-ray microimaging and microspectroscopy in the tender/hard (4–15 keV) X-ray energy range. The name PolyX comes from polycapillary X-ray optics that will be extensively used for efficient X-ray focusing and from the possibility of using polychromatic or broadband X-rays to increase the rather low flux from the SOLARIS bending magnet in the hard X-ray energy range. Polycapillary optics will provide focal spots with sizes of 8–200 μ m. Single bounce ellipsoidal capillary is expected to provide a ∼ 2 μ m focal spot size. The main experimental techniques at PolyX will be X-ray absorption and phase-contrast imaging and microtomography, micro-X-ray fluorescence imaging and micro-X-ray absorption spectroscopy. This paper presents the concept of PolyX beamline and preliminary "white" beam commissioning results. [ABSTRACT FROM AUTHOR]

In this study, the assessment of uncertainties introduced at different stages of the elemental analysis of archaeological ceramics has been described using the example of the Neolithic pottery sherds from Popovsky Lug (eastern Siberia). To evaluate the uncertainty introduced by sampling due to ceramic heterogeneity, three original sherds were cut into small subsamples. Powdered subsamples (250–350 mg) were analyzed using wavelength-dispersive X-ray fluorescence and inductively coupled plasma mass spectrometry methods, and the variations between analytical results for independent subsamples were compared with the variations introduced during the analytical process (measurement and sample preparation). It was shown that 250–350 mg of ceramic is sufficient to obtain good reproducibility (2–15%) between separate subsamples for most major and trace elements, even for the heterogeneous Neolithic ceramics included in this study. The differing behavior of concentration variations in some elements was explained by measuring the ceramic cross-sections by scanning electron microscopy and micro-X-ray fluorescence spectrometry, as well as by the theoretic modeling of the sampling error. The described workflow can be useful in finding uncertainties in elemental analysis results, which may affect the interpretation of bulk chemical composition in ceramic provenance studies. [ABSTRACT FROM AUTHOR]

A reactive transport model was employed to investigate the influence of multiple hydrate phases during acetic acid attack on Portland cement paste. The simulation accounted for the dissolution of primary cement hydrates like Ettringite, Portlandite and C-S-H, along with the formation of silica gel products impacting diffusivity. The simulations primarily utilized independent material parameters, though the effective specific surface area of C-S-H phases required adjustment, indicating that only a small fraction is active in bulk paste compared to experimental values obtained from powders. Experiments involved exposing hardened cement paste samples to acetic acid (pH = 3) for durations ranging from 35 to 84 days. The model predicted changes in mineral assemblages, porosity, and pore solution chemistry versus degradation depth and time. Comparison of calculated Ca and Si-contents with experimentally obtained values from μ XRF analysis demonstrated good agreement of within 6% error, highlighting the importance of considering multiple minerals. • Reactive transport model explores acetic acid attack (pH = 3) on cement paste. • Calibration of C-S-H effective Specific Surface Area and precipitation kinetics parameters. • Micro-XRF analysis provides concentration profiles of cement paste samples after 35–84 days for model validation. • Experimental-simulation comparison with post-processing workflow achieved 6% error. [ABSTRACT FROM AUTHOR]

Abstract Dark and clear silicate glasses formed during an iron age vitrification event ≈ 1500 years ago at the Broborg hillfort near Uppsala, Sweden have been analyzed using a scanning electron microscope equipped with a micro-X-ray fluorescence (μXRF) spectrometer. Correlated µXRF and electron beam-induced energy dispersive spectrometry (EDS) X-ray maps were collected via stage-scanning at constant velocity. This coupled procedure represents a new approach for the cultural heritage community to conduct analytical studies of archaeometric specimens composed of metal, ceramic, or mixed inorganic/organic materials, where major and trace element compositions are registered in space for areas up to the centimeter-length scale at micrometer-scale resolution. Overview images were used to select areas for EDS beam scan maps correlated with multispectral cathodoluminescence (CL) imaging and co-located quantitative EDS and μXRF point analysis. Fe, Ca, Mg, Ti, P, Mn, Zr, Zn, and Y are enriched in the dark glass, while Si, Al, K, Na, Ba, Sr, Rb, and Ga are enriched in the clear glass. Unmelted material is comprised predominately of quartz (SiO2) along with trace apatite (Ca5(PO4)3[Cl,OH]) and zircon (ZrSiO4). Multivariate statistical analysis was used to measure the area fractions of high variance components while lower variance components represented phase mixtures. Differences between calculated melt viscosities for the glass compositions are consistent with field and laboratory observations. Coupled large area EDS and μXRF imaging shows significant promise for informed selection of higher spatial resolution and higher sensitivity follow-up studies, e.g., those performed using synchrotron analysis. Graphical Abstract

The scientific examination and comparative investigation of pigments are fundamental for further understanding and analysis of historic and artistic works, and particularly useful for conservators. In fine art authentication, investigations are strongly focused on the identification of the painting materials used by the author. This study is focused on the use of non-invasive analytical techniques to increase the knowledge of the painting technique of Olga Boznańska. The aim of this study was to assess the technology, painting technique, and materials used by Olga Boznańska. The pallets, tubes with the paints, and several oil paintings were studied. For each painting, a series of images were recorded using various ranges of electromagnetic radiation, including near-infrared, visible light, ultraviolet, and X-rays. In order to characterize the pigments present in the paint layer, measurements of the elemental composition by X-ray fluorescence spectroscopy (XRF) were carried out. The ground layers and paints were measured with infrared spectroscopy (FTIR). This allowed us to identify the artist's painting technique and determine how she executed her painting, how she applied the paints, and what pigments she used. [ABSTRACT FROM AUTHOR]

Lakes in the semiarid Southern Interior Plateau of British Columbia, Canada are vulnerable to future climate-driven changes in water quantity and quality. However, few long-term monitoring records exist to assess the effects of varying hydroclimate conditions on lake function. We present a high-resolution multiproxy paleolimnological record containing subfossil diatoms, μXRF via ITRAX, and chlorophyll-a that spans the past 1800 years from Roche Lake in south-central British Columbia. Generalized additive models indicate that the diatom assemblages were associated with changes in lake level and the accompanying effects of atmospheric forcing on lake thermal structure, and that these forcing mechanisms had a weak relationship with primary production. We infer two pronounced arid periods between ca. AD 600-950 and ca. AD 1730-1950 that correspond to evidence of reduced lake mixing and enhanced anoxia, but variable patterns in primary production. Synthesis of regional proxy records suggests that inferences of moist but possibly warm conditions during the Medieval Climate Anomaly may have occurred because of a complex interaction between prolonged La Niña-like conditions and higher radiative forcing. Overall, lakes in this region are sensitive to changes in hydroclimate generated by interactions between external forcing and Pacific Ocean-atmosphere processes, and the resulting changes in aridity may have potentially negative consequences on salmonid habitat. [ABSTRACT FROM AUTHOR]

Changes in hydraulic properties of the flow are reflected in the vertical and/or lateral variation in sedimentary structures. In turbiditic sandstones, common sedimentary structures are grain size grading, planar lamination, and cross-lamination. This research is aimed at applying the advances in non-destructive X-ray fluorescence (XRF) mapping technology to detect various sedimentary structures in sandstones. XRF micro-imaging is able to produce in situ elemental–distribution maps of rock samples. This research applied a statistical technique of discriminant analysis to reduce the dimensionality of the variables in order to determine the key element intensity that can be used as a proxy for the observation of sedimentary structures in turbiditic sandstones. The results suggest that principal component analysis can identify the elements and elemental ratios with high loadings that explain the multivariate data. The sedimentary structures are shown in spatial elemental distribution maps and elemental ratios. The methodology here could be applied to in situ µXRF scans where the observation of sedimentary structures or grain size measurements is inaccessible such as in boreholes.

Dam construction across the main flow of an estuary can greatly contribute to a high accumulation of inorganic contaminants. However, it remains unknown to what extend externally available heavy metals are incorporated into biota living in those contaminated environments. In this study, the heavy metal copper was investigated both in the sediment and in the tissues of nematodes taken from the subtidal zone in the Ba Lai estuary where a dam is present, and compared with samples from the dam-free Ham Luong estuary, both part of the Mekong Delta. Samples were taken in the dry season of 2017 in four stations in the Ba Lai estuary with two stations in the downstream part from the dam and two upstream. Similar locations with respect to the distance were sampled in the dam-free estuary. The internal copper concentration in nematodes was measured by applying micro X-ray fluorescence. The results showed that both internal and sediment copper concentrations were different between the two estuaries and among estuarine sections. The highest copper concentration in nematodes was found in the upstream section of Ba Lai estuary where the greatest accumulation of sedimentary copper was observed, while the dammed downstream part was lowest in internal copper accumulation. Moreover, there was more variation in the copper levels between the two sections within the dammed estuary compared to those in Ham Luong. These observations might point to the contribution of the Ba Lai dam to the increase of copper contaminants in the benthic environment leading to accumulation in nematodes. [ABSTRACT FROM AUTHOR]

Comprehensive mineralogical and petrographic studies require analytical methods capable to report the distribution of major to trace elements within crystals in order to unravel their formation conditions and subsequent evolution. Additionally, the investigation of transition elements (e.g., Ti, V, Cr, Mn, Fe, and Zn) is essential for the comprehension of substitution processes within colored minerals. This study is conducted on a zoned kyanite crystal from a deformed quartz vein found within garnet–kyanite–biotite–hematite–plagioclase±staurolite±sillimanite paragneiss of Thassos Island, Greece. Herein, we show the efficiency of combining conventional, for example, cathodoluminescence, electron probe microanalysis (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and new methods, for example, micro-laser-induced breakdown spectroscopy (µLIBS), micro-X-ray fluorescence (µXRF), and Raman spectroscopy, to determine the chemical and crystallographic features of minerals. The simple chemistry of this crystal offers an ideal case to compare and valuate the potential of combined spectroscopy techniques to analyze minerals. We demonstrate that µLIBS and µXRF are perfectly adapted to perform multi-element imaging of major to trace elements down to the ppm level within a pluricentimetric crystal (2.3 x 0.5 cm) prior to quantitative analyses. We also highlight the benefit of cathodoluminescence and Raman mapping in the investigation of crystallographic features within minerals. The multispectroscopic approach enabled us to correlate growth stages of kyanite with the polymetamorphic history of the sample. Our results also highlight the spatial dependence of Ti for the generation of blue zonation by Fe2+–Ti4+ substitutions with Al3+. Graphical Abstract [ABSTRACT FROM AUTHOR]

Abstract Background Hyperaccumulation of trace elements is a rare trait among plants which is being investigated to advance our understanding of the regulation of metal accumulation and applications in phytotechnologies. Noccaea caerulescens (Brassicaceae) is an intensively studied hyperaccumulator model plant capable of attaining extremely high tissue concentrations of zinc and nickel with substantial genetic variation at the population-level. Micro-X-ray Fluorescence spectroscopy (µXRF) mapping is a sensitive high-resolution technique to obtain information of the spatial distribution of the plant metallome in hydrated samples. We used laboratory-based µXRF to characterize a collection of 86 genetically diverse Noccaea caerulescens accessions from across Europe. We developed an image-processing method to segment different plant substructures in the µXRF images. We introduced the concentration quotient (CQ) to quantify spatial patterns of metal accumulation and linked that to genetic variation. Results Image processing resulted in automated segmentation of µXRF plant images into petiole, leaf margin, leaf interveinal and leaf vasculature substructures. The harmonic means of recall and precision (F1 score) were 0.79, 0.80, 0.67, and 0.68, respectively. Spatial metal accumulation as determined by CQ is highly heritable in Noccaea caerulescens for all substructures, with broad-sense heritability (H2) ranging from 76 to 92%, and correlates only weakly with other heritable traits. Insertion of noise into the image segmentation algorithm barely decreases heritability scores of CQ for the segmented substructures, illustrating the robustness of the trait and the quantification method. Very low heritability was found for CQ if randomly generated substructures were compared, validating the approach. Conclusions A strategy for segmenting µXRF images of Noccaea caerulescens is proposed and the concentration quotient is developed to provide a quantitative measure of metal accumulation pattern, which can be used to determine genetic variation for such pattern. The metric is robust to segmentation error and provides reliable H2 estimates. This strategy provides an avenue for quantifying XRF data for analysis of the genetics of metal distribution patterns in plants and the subsequent discovery of new genes that regulate metal homeostasis and sequestration in plants.

Alpine subduction of a block of olivine gabbro produced a plethora of different assemblages and local structures typical of high-pressure and low-temperature metamorphism. However, gabbro with the locally well-preserved igneous assemblage olivine - augite - plagioclase occurs in some domains of a 2 km long outcrop (Allalinhorn, western Alps). A large variety of hydrate minerals including zoisite, glaucophane, talc, Mg-chloritoid, chlorite, paragonite and muscovite formed during Alpine subduction of the metagabbro. The three primary igneous minerals have been replaced by hydration reactions during Eocene subduction. Talc, omphacite, and zoisite + jadeite and are the main minerals in the local domains after olivine, augite and plagioclase respectively. The rocks preserved the coarse grained igneous texture. An excellent overview of the complex coarse textures of the eclogite facies rocks has been provided by element distribution maps produced from up to 25 cm large polished slabs of typical samples of Allalingabbro using a μXRF instrument. The RGB images suggest that the minerals formed at the high-pressure in the presence of an aqueous fluid. The pseudomorphing reactions progressed close to volume conservation. The hydration reactions required an H 2 O fluid containing dissolved solids. The mapped distribution of elements including trace elements provides important clues on the origin and mobility of these elements in the hydration fluid. The homogeneously distributed immobile Cr in omphacite portrays primary augite. The irregular patchy Sr distribution resulted from small-scale migration of components replacing plagioclase by Sr-bearing zoisite and jadeite. Coherent Ni signals are related to the presence of talc. The talc occurs as a late infill of structures produced by dissolving olivine. Mg-chloritoid, kyanite and mica coat the former grain-boundary of olivine and plagioclase suggesting that olivine dissolved at eclogite facies conditions. Talc formed at distinctly lower pressures, however, as implied by computed model reactions. The olivine replacement structures are often larger than the size thin section and can be excellently studied by the large size μXRF patterns used in this study. The fractured surroundings of the locations of olivine provided the necessary hydraulic conductivity for hydration reactions to progress. The fractures and small veinlets contain late Ni-bearing talc. Cl is only present in very late vein amphibole suggesting that hydration fluids in the subduction zone transported dissolved components as hydrous complexes (and their dissociated ions). There is no evidence for the presence of a Cl-brine during subduction. In addition to primary olivine as a local Ni source, the element may also have partly been imported with the hydration fluid and originate from dehydration of ophiolitic serpentinites in the slab. • Hydration of coarse-grained olivine-augite-plagioclase gabbro occurred during alpine subduction at high pressure and via an oxidizing Si Mg bearing saline fluid. • The coarse structures of 20 cm large slabs of the metagabbro can be analyzed using μXRF element maps. • Cr remained immobile during the augite - omphacite conversion and μXRF element maps show that Cr very clearly outlines the original igneous augite. • Ni in brittle fractures and veins is visible on large scale μXRF element maps showing that the element is mobile and present in the hydration fluid of the subduction zone in contrast to Cr. • Ni in veins can be of local origin from olivine hydration or imported with the hydration fluid from deeper in the subduction zone where ophiolitic serpentinites dehydrate. [ABSTRACT FROM AUTHOR]

In this study, benchtop micro-X-ray fluorescence spectrometry (µXRF) was evaluated as a green and cost-effective multielemental analytical technique for P. vittata. Here, we compare the arsenic (As) content values obtained from the same samples by µXRF and inductively coupled plasma-optical emissions spectrometry (ICP–OES). To obtain samples with different As concentrations, fronds at different growth time points were collected from P. vittata plants grown on two natural As-rich soils with either high or moderate As (750 and 58 mg/kg). Dried samples were evaluated using multielement-µXRF analysis and processed by PCA. The same samples were then analysed for multielement concentrations by ICP–OES. We show that As concentrations detected by ICP–OES, ranging from 0 to 3300 mg/kg, were comparable to those obtained by µXRF. Similar reliability was obtained for micro- and macronutrient concentrations. A positive correlation between As and potassium (K) contents and a negative correlation between As and iron (Fe), calcium (Ca) and manganese (Mn) contents were found at both high and moderate As. In conclusion, we demonstrate that this methodological approach based on μXRF analysis is suitable for monitoring the As and element contents in dried plant tissues without any chemical treatment of samples and that changes in most nutrient concentrations can be strictly related to the As content in plant tissue. [ABSTRACT FROM AUTHOR]

Synchrotron X-ray µ- and nano-probes are increasingly affirming their relevance in cultural heritage applications, especially in material characterization of tiny and complex micro-samples which are typical from archaeological and artistic artifacts. For such purposes, synchrotron radiation facilities are tailoring and optimizing beamlines and set-ups for CH, taking also advantages from the challenges offered by the third-generation radiation sources. In ancient ceramics studies, relevant information for the identification of production centers and manufacture technology can be obtained in a non-invasive and non-destructive way at the micro-sample level by combining different SR based methods. However, the selection of appropriate beamlines, techniques and set-ups are critical for the success of the experiments. Fine and varnished wares (e.g., Attic and western-Greek colonial products) are an excellent case study for exploring challenges offered by synchrotron X-ray microprobes optimized to collect microchemical and phase-distribution maps. The determination of provenance and/or technological tracers is relevant in correctly classifying productions, often based only on ceramic paste, gloss macroscopic features or style. In addition, when these vessels are preserved in Museums as masterpieces or intact pieces the application of non-invasive approach at the micro sample is strictly required. Well-designed synchrotron µXRF and µXANES mapping experiments are able providing relevant clues for discriminating workshops and exploring technological aspects, which are fundamental in answering the current archaeological questions on varnished Greek or western-Greek colonial products. [ABSTRACT FROM AUTHOR]

Background: Hyperaccumulation of trace elements is a rare trait among plants which is being investigated to advance our understanding of the regulation of metal accumulation and applications in phytotechnologies. Noccaea caerulescens (Brassicaceae) is an intensively studied hyperaccumulator model plant capable of attaining extremely high tissue concentrations of zinc and nickel with substantial genetic variation at the population-level. Micro-X-ray Fluorescence spectroscopy (µXRF) mapping is a sensitive high-resolution technique to obtain information of the spatial distribution of the plant metallome in hydrated samples. We used laboratory-based µXRF to characterize a collection of 86 genetically diverse Noccaea caerulescens accessions from across Europe. We developed an image-processing method to segment different plant substructures in the µXRF images. We introduced the concentration quotient (CQ) to quantify spatial patterns of metal accumulation and linked that to genetic variation. Results: Image processing resulted in automated segmentation of µXRF plant images into petiole, leaf margin, leaf interveinal and leaf vasculature substructures. The harmonic means of recall and precision (F1 score) were 0.79, 0.80, 0.67, and 0.68, respectively. Spatial metal accumulation as determined by CQ is highly heritable in Noccaea caerulescens for all substructures, with broad-sense heritability (H2) ranging from 76 to 92%, and correlates only weakly with other heritable traits. Insertion of noise into the image segmentation algorithm barely decreases heritability scores of CQ for the segmented substructures, illustrating the robustness of the trait and the quantification method. Very low heritability was found for CQ if randomly generated substructures were compared, validating the approach. Conclusions: A strategy for segmenting µXRF images of Noccaea caerulescens is proposed and the concentration quotient is developed to provide a quantitative measure of metal accumulation pattern, which can be used to determine genetic variation for such pattern. The metric is robust to segmentation error and provides reliable H2 estimates. This strategy provides an avenue for quantifying XRF data for analysis of the genetics of metal distribution patterns in plants and the subsequent discovery of new genes that regulate metal homeostasis and sequestration in plants. [ABSTRACT FROM AUTHOR]

This work reveals, by imaging in vivo measurements in the Cd/Zn hyperaccumulator Arabidopsis halleri , in how far Cd stress affects macronutrient (Ca, K) and micronutrient (Fe, Zn) distribution in the leaves. We directly correlate these changes with biophysics of the photosynthetic light reactions. Plants were grown for 2 months at 10 μM Zn (=control), and supplemented with 10, 15, 50 or 75 μM Cd. Direct imaging of OJIP transients revealed that bundle sheath cells were more sensitive to Cd toxicity than mesophyll cells further from the vein. Progressive inhibition of photosystem (PS) II reaction centres and decrease in quantum yield of electron transport between Q A and Q B and further to PSI acceptors was observed. This was correlated with the decreased dynamics of Q A re-oxidation and lower operating efficiency of PSII. Analysis by a benchtop micro X-ray fluorescence device showed that Cd mostly accumulated in the veins, and restricted Fe and Zn distribution from the veins, especially in the 75 μM Cd, while K concentration increased in the whole leaf. Calcium distribution was apparently not affected by Cd, but Cd excess inhibited trichome formation and thereby diminished total Ca concentration in the leaves. The results point to differential tissue sensitivity to Cd, evident by heterogeneous inhibition of photosynthesis. Part of this may be a result of selective disturbances in the leaf nutrient homeostasis. The better photosynthetic performance away from the veins compared to the bundle sheath cells, however, indicates that direct inhibition of photosynthesis by Cd dominates over inhibition caused by micronutrient deficiency. Image 1 • OJIP transients show higher Cd sensitivity in the veins than in the mesophyll. • Cd was accumulated more in the veins than in the mesophyll. • Cd inhibited Fe and Zn distribution between the veins, bundle sheath and mesophyll. • Direct inhibition of photosynthesis by Cd dominates over inhibition by malnutrition. [ABSTRACT FROM AUTHOR]

A common issue in non-destructive surface analysis of historical silver coins is depletion of Cu from the near-surface areas, which in turn results in higher Ag content at a coin's surface. This paper reports a non-destructive analytical strategy using µXRF for identification of Ag and Cu surface enrichments and depletions by comparing peak intensity ratios of Ag Kα/Ag Lα, Cu Kα/Ag Kα and Cu Lα/Ag Lα for coins and Ag-Cu standards of similar composition. Our characterization of coins from different contexts and chronologies shows that a multi-standard approach provides the most reliable identification of surface enrichment of Ag and depletion of Cu. Coins possessing Ag surface enrichment were further analysed with LA-ICP-MS to determine any differences in trace element composition between the cores and surface of the coins. We show that the near-surface regions of these coins are enriched in Au and depleted in Co, Ni, As, and Pt relative to their cores. These systematics allow for a more robust assessment of the degree of silver coin surface alteration critically important in measuring the original composition of historical silver coins. [ABSTRACT FROM AUTHOR]

Summary: Like pathogens, beneficial endophytic fungi secrete effector proteins to promote plant colonization, for example, through perturbation of host immunity. The genome of the root endophyte Serendipita indica encodes a novel family of highly similar, small alanine‐ and histidine‐rich proteins, whose functions remain unknown. Members of this protein family carry an N‐terminal signal peptide and a conserved C‐terminal DELD motif.Here we report on the functional characterization of the plant‐responsive DELD family protein Dld1 using a combination of structural, biochemical, biophysical and cytological analyses.The crystal structure of Dld1 shows an unusual, monomeric histidine zipper consisting of two antiparallel coiled‐coil helices. Similar to other histidine‐rich proteins, Dld1 displays varying affinity to different transition metal ions and undergoes metal ion‐ and pH‐dependent unfolding. Transient expression of mCherry‐tagged Dld1 in barley leaf and root tissue suggests that Dld1 localizes to the plant cell wall and accumulates at cell wall appositions during fungal penetration. Moreover, recombinant Dld1 enhances barley root colonization by S. indica, and inhibits H2O2‐mediated radical polymerization of 3,3′‐diaminobenzidine.Our data suggest that Dld1 has the potential to enhance micronutrient accessibility for the fungus and to interfere with oxidative stress and reactive oxygen species homeostasis to facilitate host colonization. [ABSTRACT FROM AUTHOR]

A combined approach based on multiple X-ray analytical techniques and conventional methods was adopted to investigate the distribution and speciation of Cr in a polluted agricultural soil, from the bulk-scale down to the (sub)micro-level. Soil samples were collected from two different points, together with a control sample taken from a nearby unpolluted site. The bulk characterization revealed that the polluted soils contained much higher concentrations of organic matter (OM) and potentially toxic elements (PTE) than the control. Chromium was the most abundant PTE (up to 5160 g kg−1), and was present only as Cr(III), as its oxidation to Cr(VI) was hindered by the high OM content. According to sequential extractions, Cr was mainly associated to the soil oxidisable fraction (74%) and to the residual fraction (25%). The amount of Cr potentially bioavailable for plant uptake (DTPA-extractable) was negligible. Characterization of soil thin sections by micro X-ray fluorescence (μXRF) and field emission scanning electron microscopy coupled with microanalysis (FEGSEM-EDX) showed that Cr was mainly distributed in aggregates ranging from tens micrometres to few millimetres in size. These aggregates were coated with an aluminosilicate layer and contained, in the inner part, Cr, Ca, Zn, P, S and Fe. Hyperspectral elaboration of μXRF data revealed that polluted soils were characterised by an exogenous organic-rich fraction containing Cr (not present in the control), and an endogenous aluminosilicate fraction (present also in the control), coating the Cr-containing aggregates. Analyses by high-resolution micro X-ray computed tomography (μCT) revealed a different morphology of the soil aggregates in polluted soils compared with the control. The finding of microscopic leather residues, combined with the results of bulk- and micro-characterizations, suggested that Cr pollution was likely ascribable to soil amendment with tannery waste-derived matrices. However, over the years, a natural process of Cr stabilization occurred in the soil thus reducing the environmental risks. [ABSTRACT FROM AUTHOR]

Paspalum urvillei and Setaria parviflora are two plant species naturally adapted to iron-rich environments such as around iron mines wastes. The aim of our work was to characterize how these two species cope with these extreme conditions by comparing them with related model species, Oryza sativa and Setaria viridis, that appeared to be much less tolerant to Fe excess. Both Paspalum urvillei and Setaria parviflora were able to limit the amount of Fe accumulated within roots and shoots, compared to the less tolerant species. Perls/DAB staining of Fe in root cross sections indicated that Paspalum urvillei and Setaria parviflora responded through the build-up of the iron plaque (IP), suggesting a role of this structure in the limitation of Fe uptake. Synchrotron μXRF analyses showed the presence of phosphorus, calcium, silicon and sulfur on IP of Paspalum urvillei roots and μXANES analyses identified Fe oxyhydroxide (ferrihydrite) as the main Fe form. Once within roots, high concentrations of Fe were localized in the cell walls and vacuoles of Paspalum urvillei , Setaria parviflora and O. sativa whereas Setaria viridis accumulated Fe in ferritins. The Fe forms translocated to the shoots of Setaria parviflora were identified as tri-iron complexes with citrate and malate. In leaves, all species accumulated Fe in the vacuoles of bundle sheath cells and as ferritin complexes in plastids. Taken together, our results strongly suggest that Paspalum urvillei and Setaria parviflora set up mechanisms of Fe exclusion in roots and shoots to limit the toxicity induced by Fe excess. • Paspalum urvillei and Setaria parviflora are two species naturally adapted to iron-rich environments. • These two species are more tolerant to Fe excess than the model, related species Oryza sativa and Setaria viridis. • Tolerance to Fe excess is achieved by exclusion: formation of iron plaque and vacuolar storage in roots. • The iron plaque is composed mostly of ferrihydrite; Fe is translocated in xylem as tri-Fe citrate-malate complexes. [ABSTRACT FROM AUTHOR]

Ancient maritime trading ports along the southern coast of Oman have been the target of archaeological excavations for several decades. Though historical chronologies are well-researched, information from a paleoenvironmental perspective is lacking and can provide a more complete understanding of site development. This study investigates the timing of coastal sand barrier accumulation in the natural harbours at Khor Al Balid and Khor Rori, which had considerable effects on the populations at the ancient cities of al–Balīd and Sumhuram, respectively. Six cores from Khor Al Balid and four cores from Khor Rori were analyzed using sedimentological, microfossil (foraminifera and testate amoebae), geochemical (μXRF), and radiocarbon dating methods. Marine proxies (e.g., Amphistegina spp., C. pseudolobatulus , E. limbatum , Sr, Ca/Si) and lagoon proxies (e.g., T. macrescens , T. inflata , C. constricta and C. aculeata , Ti/Ca, Fe/Ca) were used to identify Marine Sand, Brackish Lagoon/Marsh, and Freshwater facies. Results indicate that the eastern arm of Khor Al Balid closed off from the sea around the 12th century CE and that the western arm closed around the 15th century CE. Siltation of harbours and the formation of sand barriers may have contributed towards site abandonment. Previous archaeological findings suggest that al-Balīd was able to continue with maritime trade activities along the southern seaside edge of the city for several centuries after siltation of Khor Al Balid, possibly with the help of dredging. An extreme overwash event was recorded in almost all cores across both sampling sites, suggesting that a very large cyclone or a tsunami hit the southern Oman coast sometime around the 18th–19th century CE. This event, as well as continuous coastal sand accumulation, may have contributed to the decline and abandonment of Khor Al Balid and highlights the impacts that large storm/wave events have on archaeological site preservation. • Microfossils and μXRF suggest closure of Al Balid's natural harbour ∼12–15th c. CE • Results indicate an extreme overwash event ∼18–19th c. CE along the Dhofar coast • Environmental changes may have contributed to the decline of the two port sites [ABSTRACT FROM AUTHOR]

The construction of harbours along high energy nearshore environments, which commonly include the emplacement of hard structures both as central features (e.g., piers, jetties) as well as protective measures (e.g., wave breakers, coastal armouring), can alter coastlines in a multitude of ways. These include reconfiguring the coast's morphology, introducing or redistributing exogenous and endogenous materials, and changing localized environmental substrate and structural conditions; and, as a result, impact the associated ecological communities. With growing coastal populations and associated coastal development, concerns over the long-term consequences of such projects are of global interest. Caesarea Maritima, a large-scale, artificially constructed ancient harbour built between 21 and 10 BCE, provides a rare opportunity to address these impacts and investigate its fingerprint on the landscape over 2000 years. To approach this, representative sediment samples were isolated and analyzed from two sediment cores (C1, C2), an excavated trench (W), and a sample of ancient harbour construction material (aeolianite sandstone and hydraulic concrete; COF). Geochemical (Itrax μXRF, magnetic susceptibility) and foraminifera analyses were conducted and results from both methods were statistically grouped into significantly similar clusters. Results demonstrated the increased presence of aeolianite-associated elemental contributions only after the construction of Caesarea as well as in particularly high concentrations following previously proposed tsunami events, during which shallower and deeper materials would have been transported and redeposited. The foraminifera data shows the appearance and eventual abundance dominance of Pararotalia calcariformata as an indicator of coastal hardening. Results suggest that they are an especially well-suited species to demonstrate changing environmental conditions existing today. In previous studies, this species was mistakenly presented as a recent Lessepsian arrival from the Red Sea, when in fact it has had a long history as an epiphyte living on hardgrounds in the Mediterranean and co-existencing with humans and their harbour-building habits. Specimens of P. calcariformata , therefore, are useful indicators for the timing of harbour construction at Caesarea and may be used as rapid and cost-effective biostratigraphic indicators on sandy nearshore coastline in future geoarchaeological studies. This has implications for future studies along the Israeli coast, including both paleoenvironmental and modern ecological assessments. • Epiphytic forams are cost-effective biostratigraphic tools on sandy coasts. • P. calcariformata is not a recent lessepsian arrival from the Red Sea. • Epiphytic forams and harbour material can indicate long-term sediment transport. [ABSTRACT FROM AUTHOR]

Synchrotron X-ray µ- and nano-probes are increasingly affirming their relevance in cultural heritage applications, especially in material characterization of tiny and complex micro-samples which are typical from archaeological and artistic artifacts. For such purposes, synchrotron radiation facilities are tailoring and optimizing beamlines and set-ups for CH, taking also advantages from the challenges offered by the third-generation radiation sources. In ancient ceramics studies, relevant information for the identification of production centers and manufacture technology can be obtained in a non-invasive and non-destructive way at the micro-sample level by combining different SR based methods. However, the selection of appropriate beamlines, techniques and set-ups are critical for the success of the experiments. Fine and varnished wares (e.g., Attic and western-Greek colonial products) are an excellent case study for exploring challenges offered by synchrotron X-ray microprobes optimized to collect microchemical and phase-distribution maps. The determination of provenance and/or technological tracers is relevant in correctly classifying productions, often based only on ceramic paste, gloss macroscopic features or style. In addition, when these vessels are preserved in Museums as masterpieces or intact pieces the application of non-invasive approach at the micro sample is strictly required. Well-designed synchrotron µXRF and µXANES mapping experiments are able providing relevant clues for discriminating workshops and exploring technological aspects, which are fundamental in answering the current archaeological questions on varnished Greek or western-Greek colonial products.

This paper presents a new non-destructive sampling method for the lead isotope analysis of lead objects using acidified cotton swabs. The results are indistinguishable within error margin from conventional sampling methods. This method was applied to a series of Sasanian lead coins from the Royal Museums of Art and History as well as a private collection. Elemental analysis was performed using micro-X-ray fluorescence. Isotopic analysis was performed using multi collector-inductively coupled plasma-mass spectrometry. Lead isotope analysis showed that at least four distinct sources of lead were used over time by the Sasanians to produce coins. Elemental analysis revealed three compositional groups distinct from the isotope groups, showing that a change in composition did not necessarily follow a change in raw materials supply. The uniformity of isotope compositions within particular periods, and of chemical composition across different mints, may point to a central control of both raw material supply and composition of Sasanian lead coins. [ABSTRACT FROM AUTHOR]

This paper presents the analysis of decoloured and naturally coloured glass from well-dated contexts in the southwest corner of the Roman fort at Oudenburg (Belgium) ranging from the late second to the early fifth century AD. The aim is three-fold. First, provide comparative material in the study of glass consumption from the northwestern provinces of the Roman Empire. Secondly, evaluate possible diachronic shifts in the applied decolourizing agent to produce colourless glass as to assess potential correlations between glass production recipes, provenance and chrono-typology. Finally, provide an added value to the research of glass recycling and mixing in the Roman imperial period. Nine subgroups are distinguished based on their chemical composition determined by LA-ICP-MS: Sb-only, two groups of Mn-only, four groups of mixed Mn-Sb, HIMT and one glass without any decolouring agent. The Sb-decoloured glass is used in the earliest phases and can be attributed to an Egyptian provenance. The two subgroups of Mn-glass likely come from different provenances: one from Egypt and the other later one from the Levant. Most of the glass shows high marks of mixing based on high trace elements concentrations and the simultaneous presence of antimony and manganese. Inhomogeneous mixing of manganese and antimony was also detected through μXRF. One Mn-Sb subgroup likely comes from mixing antimony glass with HIMT. The obtained results help better recognise the shifts in applied glass recipes throughout the Roman imperial period and improve our understanding about the mixing and recycling of glass to supply a Roman military camp. [ABSTRACT FROM AUTHOR]

Silicon, while not an essential element, is known to have positive roles in certain vegetable species. For instance, it has been recognized to protect them from biotic and abiotic stress. Due to the fact that certain species accumulate the aforementioned element in their tissues, the determination of its concentration is of importance in different disciplines, such as dendrology, plant physiology, forest management, agroecology, and also in the wood industry. Usually, its quantification is preceded by a series of digestion steps that, aside from been time-consuming, and contamination-prone, prevents from conducting a spatial distribution of the element on the sample. In this research, samples of Pinus radiata wood were studied using a synchrotron radiation source that allowed direct scanning of its surface without any treatment, and the determination of silicon as a function of the position and the tree rings, using micro X-ray fluorescence (µXRF). A quantification method based in the fundamental parameters approach was evaluated. It was found that silicon concentration increases near the latewood ring zones, showing a periodical behavior, related to seasonal environmental events. [ABSTRACT FROM AUTHOR]

Pseudotachylytes, produced by frictional heating during seismic slip, convey information that is critical to understanding the physics of earthquakes, their geochemical features triggered by frictional melting shed light on the seismic processes and frictional strength as well. However, whether their geochemical properties changed during exhumed process is still uncertain. To provide insight to this topic, we conducted a case study of pseudotachylytes in the Longmen Shan thrust belt, eastern Tibet. Pseudotachylyte samples drilled from the WFSD boreholes at deep depth and collected at surface outcrops were analyzed by μXRF core scanner to estimate their geochemical variations. Macro- and micro-structural observations suggest that the pseudotachylytes are from melt-origin. Comparative analyses of the geochemical characteristics between surface and deep pseudotachylytes show that the former are K- and Ti-depleted in an oxidation environment, while the latter have low Si, high K, Fe, Ti and Mn in a reductive environment. Besides the selective melting process, another reasonable explanation for these differences is that the geochemical properties of the surface pseudotachylytes have changed due to the prolonged fluid influence during the long-term exhumation processes, which cannot exactly reflect the nature of the initial frictional melt. Therefore, we conclude that primary pseudotachylytes are characterized by enrichment of K, Fe, Ti, Mn and depletion of Si. The frictional melt was generated in high-temperature reductive environment, and fluids have influenced their chemical composition during the exhumation process. These results are of great significance for correctly understanding earthquake mechanics and fault behavior. [ABSTRACT FROM AUTHOR]

A combination of Itrax micro-X-ray fluorescence core scanning (μXRF-CS) and freeze coring can facilitate the development of high-resolution (e.g. sub-decadal) paleoclimate records in lacustrine systems where low sedimentation rates and poorly consolidated "colloidal soup" at the sediment/water interface prevents retrieval and Itrax-μXRF-CS analysis of undisturbed cores using conventional gravity corers. The iBox-FC containment vessel described and tested here delays thawing of highly perishable freeze cores for up to two hours, providing adequate time to carry out high-resolution Itrax-μXRF-CS analysis. The iBox-FC is comprised of an open-topped Styrofoam box divided into chambers using high-density polyethylene (HDPE) that are filled with freeze pack gel. When the vessel is frozen, core slabs up to 13 cm long may be positioned into a central chamber and then scanned following normal Itrax-μXRF-CS methodology. To test the reliability of μXRF-CS analysis obtained from frozen sediments, a freeze core recovered from Control Lake, Northwest Territories, Canada, was sub-sectioned and analyzed using μXRF-CS and then subsampled for ICP-MS following near-total acid digestion. Comparison of μXRF-CS and ICP-MS results showed strong correlations (R2 > 0.8) for six of nine elements calibrated, and moderate correlations (R2 > 0.3) for the remaining three. Additive log-ratio transformation of data minimized specimen, matrix and edge effects associated with the high porewater contents of the freeze cores and slight melting of the sediment during analysis. These analytical effects had more impact on the lower concentration elements (As, Zn, Ni, Cu) than the higher concentration elements (Ti, K, Mn, Fe, Ca). [ABSTRACT FROM AUTHOR]

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Abstract Lake Suigetsu (Japan) is a key site for radiocarbon (14C) calibration and palaeo-environmental reconstruction in East Asia. Here we present a description of the sediment (micro)facies, which in combination with a new approach to varve interpolation allows construction of a revised varve based chronology that extends the previous 2012 varve based chronology by ∼10 ka, back to ∼50 ka BP. Challenges in varve counting and interpolation, which were previously discussed in detail only for the Last Glacial-Interglacial Transition, are described here back to ∼50 ka BP. Furthermore, the relative merits of varve counting by μXRF scanning and by thin-section microscopy are discussed. Facies analysis reveals four facies zones, their transitions driven by both local and climatic controls. The lamination quality of the sediment is highly variable and varve interpolation reveals that in the analysed time interval, on average, only 50% of the annual cycles are represented by seasonal layers. In the remaining years seasonal layers are indistinguishable, i.e. either did not form or were not preserved. For varve interpolation an advanced version of the Varve Interpolation Program was used, which enabled the construction of the longest, purely varve dated chronology published, despite long intervals of poor lamination quality. The calculated interpolation uncertainty is +8.9% and −4.6%, which is well within expectations considering the high degree of interpolation and the length of the record. Highlights • New facies and microfacies data from Lake Suigetsu are presented. • Analysis covers the time frame from 50 to 10 ka BP. • Detailed description varve characteristics for the complete analysed interval. • Discussion of μXRF as a tool for varve counting compared to microscope counting. • Detailed discussion of strength and weaknesses of the Suigetsu varve chronology. [ABSTRACT FROM AUTHOR]

Abstract At present, knowledge of late Quaternary variability of the Indonesian-Australian summer monsoon in the Australian tropics is limited. Organic spring deposits, which occur throughout the Kimberley region of northwest Australia, are valuable archives that contain records spanning the past ∼14,500 years. In this study we compare multiple proxies from three organic springs. Principal Components Analyses demonstrates similar patterns of change in the elemental and non-pollen palynomorph (NPP) datasets between the springs, implying regional drivers are responsible for changes in these proxies. By comparison, the pollen records differ between each of the springs, with the assemblage at each thought to be influenced by spring recharge and evolution rather than climate variability. In order to empirically and objectively assess the synchronicity of changes, we applied Monte Carlo empirical orthogonal function (MCEOF) analysis to one variable in each μXRF and NPP dataset (Si/Ti ratios and Pseudoschizaea accumulation rates, as these proxies are expected to reflect hydrological conditions in springs) to assess regional patterns of change in site moisture. This analysis revealed periods of increased monsoonal precipitation from ∼14,500–7500 cal. yr BP corresponding with deglacial sea level rise, high orbital tilt coupled with warmer sea surface temperatures, and with possible links to a southward migration of the Inter Tropical Convergence Zone (ITCZ) during the Younger Dryas. Monsoonal precipitation was reduced from 7500 cal. yr BP coinciding with the culmination of deglacial sea level rise and a possible northward shift in the mean position of the ITCZ, in addition to between 2600 and 1000 cal. yr BP corresponding with increased moderate-to-strong ENSO events. Highlights • Three new organic spring records from northwest Australia spanning the last ∼14,500 years. • Multi-proxy/site study determines genuine inter-site coherency (regional trends). • Records provide evidence of Indonesian-Australian Summer Monsoon variability since the deglacial. • Increased monsoon precipitation from 14,500 yr BP, weaker monsoon 2600–1000 yr BP. • Highlights benefits of multi-site approach in avoiding over-interpreting a single record. [ABSTRACT FROM AUTHOR]

Very small, green colored, partially mummified remains of a perinate individual were found buried in a ceramic pot with a copper coin in the Late Medieval cemetery of Nyárlőrinc-Hangár út (“Nyárlőrinc 3. lelőhely”) in southern Hungary. The remains must date back to the second half of the nineteenth century AD. In this paper; we present data gathered in a series of multidisciplinary investigations targeted to the partially mummified remains (ind. no. 14426) and two other non-mummified perinates (ind. no. 10662 and no. 14336) possibly buried under similar circumstances in the cemetery. Besides standard macromorphological and stereomicroscopic examinations, we compared Cu concentrations in the remains using ICP-AES and mapped Cu concentration changes using μXRF. The partially mummified perinate showed the highest Cu concentrations, while the individual buried without a possible Cu source showed the lowest. Body parts in the closer proximity of the copper coins always showed higher concentration. The mummified individual showed 497 times higher Cu values than average, and even the perinate buried without copper coin measured higher than the otherwise normal Cu content of the soil. Extremely high Cu values may be related to the corrosion of the coins included in the burials. Mummification must have been facilitated by copper deriving from the coins. Uneven Cu concentrations and only partial mummification of one of the individuals refer to the importance of other environmental factors involved in a possible quasi-natural mummification process. However, the Nyárlőrinc perinate burial no. 14426 may be the first solely copper-driven mummification case ever reported, and hopefully, more cases are to appear in the future. [ABSTRACT FROM AUTHOR]

• Casparian bands were developed in the central part of the root tip in the highest Cu and Zn treatments. • Preferential accumulation of Fe and Mn was localized in the root cap, while other studied elements (Ca, Cu, Ni, and Zn) were localized in the root tip. • Copper negatively affected measured photosynthetic parameters Φ Po and Φ ET2o more than zinc. Pollution by potentially toxic trace metals, such as copper or zinc, is global. Both Cu and Zn are essential microelements, which in higher concentrations become toxic. The aquatic plant Pistia stratiotes (L. has great potential for phytoremediation. Also, it has an unusually large and easily detachable root cap, which makes it a suitable model for studying the potential role of the root cap in metal uptake. Plant response to environmentally relevant concentrations of Cu (0.1, 0.3, and 1 μM) and Zn (0.3, 1, and 3 μM) was investigated with the aim of studying their interaction and distribution at the root tissue level as well as revealing their tolerance mechanisms. Changes in the root anatomy and plant ionome were determined using light and fluorescence microscopy, ICP-MS, and μXRF imaging. Alterations in photosynthetic activity caused by Cu or Zn excesses were monitored by direct imaging of fast chlorophyll fluorescence kinetics (OJIP). Fe and Mn were preferentially localized in the root cap, while Ca, Cu, Ni, and Zn were mainly in the root tip regardless of the Cu/Zn treatment. Translocation of Cu and Zn to the leaves increased with higher doses, however the translocation factor was the lowest in the highest treatments. Measurements of photosynthetic parameters showed a higher susceptibility of electron transport flux from Q A to Q B under increasing Cu than Zn supply. This, along with our findings regarding the root anatomy and the differences in Ca accumulation and distribution, led to the conclusion that P. stratiotes is more effective for Zn remediation than Cu. [Display omitted] [ABSTRACT FROM AUTHOR]

Geochemical proxy records from calcite shells of bivalves constitute an important archive for the reconstruction of palaeoenvironmental conditions on sub-annual timescales. However, the incorporation of these trace element and stable isotope proxies into the shell is influenced by a multitude of physiological and environmental factors that need to be disentangled to enable reliable reconstruction of palaeoclimate and palaeoenvironment. In this study, records of multiple proxies in three bivalve taxa from the same late Campanian locality in Oman are used to study the expression of various geochemical proxies in relation to each other and to the palaeoenvironment. Micro-X-Ray Fluorescence mapping allows the localization, discussion and evasion of diagenetically altered parts of the fossil shells. X-Ray Fluorescence line scanning calibrated with Laser Ablation Inductively Coupled Plasma Mass Spectrometry is used to measure trace element profiles through well-preserved calcitic parts of the shells. Records of stable carbon and oxygen isotope ratios of shell calcite are combined with these high-resolution trace element concentration profiles to study sub-annual variations in shell chemistry and reconstruct changes in the palaeoenvironment of the bivalves on a seasonal scale. Spectral analysis routines are used to detect cyclicity in stable isotope (δ 18 O and δ 13 C) and trace element (Mg/Ca, Sr/Ca, S/Ca and Zn/Ca) records. Differences in seasonal expression between these chemical proxies and between individual shells are discussed in terms of the relative influence of palaeoenvironment and potential species-specific physiological effects. Stable oxygen isotope ratios between shells suggest a local palaeotemperature seasonality of 8 °C around an annual mean of 28 °C, with the shell of the rudistid Torreites sanchezi milovanovici yielding slightly higher average temperatures. The discussion of the application of various Mg/Ca palaeotemperature calibrations on Mg/Ca records in these bivalve species emphasizes the complexity of using trace element proxies in extinct bivalve species. It shows that long-term changes in Mg/Ca ratios in ocean water need to be taken into account and that Mg/Ca ratios in bivalves might be influenced by vital effects. Sr/Ca and S/Ca ratios in these fossil taxa are likely controlled by growth and metabolic rates of the shell, although an influence of local salinity on strontium-to-calcium ratios cannot be excluded. Sub-annual variations in zinc concentrations in shell calcite may reflect seasonal variations in palaeoproductivity and redox conditions in the water column. [ABSTRACT FROM AUTHOR]