Nanoscale trace metal imprinting of biocalcification of planktic foraminifers by Toba's super-eruption.

Bioactive metal releases in ocean surface water, such as those by ash falls during volcanic super-eruptions, might have a potentially toxic impact on biocalcifier planktic microorganisms. Nano-XRF imaging with the cutting-edge synchrotron hard X-ray nano-analysis ID16B beamline (ESRF) revealed for the first time a specific Zn- and Mn-rich banding pattern in the test walls of Globorotalia menardii planktic foraminifers extracted from the Young Toba Tuff layer, and thus contemporaneous with Toba's super-eruption, 74,000 years ago. The intra-test correlation of Zn and Mn patterns at the nanoscale with the layered calcareous microarchitecture, indicates that the incorporation of these metals is syngenetic to the wall growth. The preferential Mn and Zn sequestration within the incipient stages of chamber formation suggests a selective incorporation mechanism providing a resilience strategy to metal pollution in the test building of planktic foraminifers.

Perspectives on heterococcolith geochemical proxies based on high-resolution X-ray fluorescence mapping.

Heterococcoliths are micron-scale calcite platelets produced by coccolithophores. They have been the most abundant and continuous fossil record over the last 215 million years (Myr), offering great potential for geochemical studies, although the heterococcolith fossil record remains underutilised in this domain. We have mapped heterococcoliths' composition using X-ray fluorescence (XRF) with a 100-nm resolution beam to decipher element distributions in heterococcoliths and to investigate the potential development of geochemical proxies for palaeoceanography. The study presents two Middle Jurassic Watznaueria britannica heterococcoliths from Cabo Mondego, Portugal. XRF analysis was performed with a 17 keV incident energy beam at the European Synchrotron Radiation Facility ID22NI beamline to study elements from Sr down to S. Ca, Sr and Mn are distributed following the heterococcolith crystalline arrangement. Cl, Br and S display an homogeneous distribution, whereas K, Fe, Cu, Zn and Rb are concentrated at the edges and in the central area of the heterococcoliths. Distributions of K, Fe, Ti, Fe, Cu, Zn, Rb and to a lesser extent V and Cr are highly influenced by clay contamination and peripheral diagenetic overgrowth. Mn is related to diagenetic Mn-rich CaCO3 overgrowth on top of or between heterococcoliths shields. Cl and Br are likely to be present in heterococcoliths inside interstitial nano-domains. We assume that the cytoplasm [Cl(-) ] and [Br(-) ] are mediated and constant during heterococcolithogenesis. Assuming a linear correlation between cytoplasm [Cl(-) ] and sea water [Cl(-) ], heterococcolith Cl may have potential as a salinity proxy. As S is incorporated into heterococcoliths by sulphated polysaccharides, our study suggests a role for such polysaccharides in heterococcolithogenesis for at least 170 Myr. The low Sr/Ca in the W. britannica specimens studied here may either highlight an unusual cellular physiology of Mesozoic coccolithophores or result from low growth rates in oligotrophic environments.

Implementation of X-ray fluorescence microscopy for investigation of elemental abnormalities in amyotrophic lateral sclerosis.

The abnormalities of metallochemical reactions may contribute to the pathogenesis of Amyotrophic Lateral Sclerosis (ALS). In the present work, an investigation of the elemental composition of the gray matter, nerve cells and white matter from spinal cord tissues representing three ALS cases and five non-ALS controls was performed. This was done with the use of the synchrotron microbeam X-ray fluorescence technique (micro-SRXRF). The following elements were detected in the tissue sections: P, S, Cl, K, Ca, Fe, Cu, Zn and Br. A higher accumulation of Cl, K, Ca, Zn and Br was observed in the nerve cell bodies than in the surrounding tissue. Contrary to all other elements, Zn accumulation was lower in the white matter areas than in the gray matter ones. The results of quantitative analysis showed that there were no general abnormalities in the elemental accumulation between the ALS and the control group. However, for individual ALS cases such abnormalities were observed for the nerve cells. We also demonstrated differences in the elemental accumulation between the analyzed ALS cases.

ID22: a multitechnique hard X-ray microprobe beamline at the European Synchrotron Radiation Facility.

The ID22 beamline is dedicated to hard X-ray microanalysis allowing the combination of fluorescence, spectroscopy, diffraction and tomography techniques in a wide energy range from 6 to 70 keV. The recent installation of an in-vacuum undulator, a new sample stage and the adaptation of various focusing optics has contributed to a great improvement in the capabilities of the beamline, which is now accessed by a wide user community issued from medical, earth and environmental science, archaeology and material science. Many applications requiring low detection limits for localization/speciation of trace elements together with structural analysis have been developed at the beamline on the (sub)micrometer scale. The possibility of combining simultaneously different analytical probes offers the opportunity of a thorough study of a given sample or scientific problem. This paper presents a review of the recent developments of the beamline and a detailed description of its capabilities through examples from different fields of applications.

Quantification of single fluid inclusions by combining synchrotron radiation-induced micro-X-ray fluorescence and transmission.

Fluid inclusions represent the only direct samples of ancient fluids in many crustal rocks; precise knowledge of their chemical composition provides crucial information to model paleofluid-rock interactions and hydrothermal transport processes. Owing to its nondestructive character, micrometer-scale spatial resolution, and high sensitivity, synchrotron radiation-induced micro-X-ray fluorescence has received great interest for the in situ multielement analysis of individual fluid inclusions. Major uncertainties associated with the quantitative analysis of single fluid inclusions arise from the inclusion depth and the volume of fluid sampled by the incident beam. While the depth can be extracted directly from the fluorescence spectrum, its volume remains a major source of uncertainty. The present study performed on natural and synthetic inclusions shows that the inclusion thickness can be accurately evaluated from transmission line scans. Experimental data matched numerical simulations based on an elliptical inclusion geometry. However, for one nonelliptical inclusion, the experimental data were confirmed using a computed absorption tomography reconstruction. Good agreement between the imaging and scanning techniques implies that the latter provides reliable fluid thickness values independent of the shape of the inclusion. Taking into consideration the incident angle, the incident beam energy, the inclusion fluid salinity, and the transmission measurement stability resulted in errors of 0.3-2 microm on calculated fluid inclusion thicknesses.

Microbeam synchrotron imaging of hairs from ancient Egyptian mummies.

Developments in microfocus synchrotron techniques have led to new results regarding the long-term alteration of archaeological samples of biological origin. Here, ancient hair samples from two Egyptian mummies have been analyzed using a conjunction of structural and elemental synchrotron methods. In this favored context of conservation, structural analysis revealed a remarkable preservation of keratin supramolecular organization at any observed length scale. Bulk keratin structure has therefore not been modified significantly over 2000 years. However, infrared spectroscopy indicated a partial disorganization of keratins close to the hair surface through polypeptide bond breakage. Elemental mapping showed a strongly heterogeneous distribution which can be related to mummification and cosmetic treatments.

Lead-revealed lipid organization in human hair.

Human hair lipids form a complex mixture of composition close to that of sebum. Part of these lipids appears in an organized state that has been studied by diffraction techniques in the literature. Nevertheless, information on the structure of these lipids remains very scarce due to their low contribution to global hair diffraction pattern. Here we show that appropriate lead treatment considerably enhances organized lipid features observed by microbeam synchrotron radiation diffraction experiments. We attribute these features to the formation of lead soaps of free fatty acids. Specific orientation of hair "lipid crystals" in planes parallel to the hair axis is clearly demonstrated. Inclusion of these lipids in the bulk of the hair shaft is shown by diffraction experiments following removal of the cuticular outermost layer of hair. Moreover, microfluorescence and diffraction experiments are consistent with part of the lipids being present as calcium soaps in native hair. We therefore consider lead fixation as a powerful tool to evaluate the lipid organization in human hair for medical, environmental and archaeological purposes, including lead poisoning.

Lack of cell death enhancement after irradiation with monochromatic synchrotron X rays at the K-shell edge of platinum incorporated in living SQ20B human cells as cis-diamminedichloroplatinum (II).

In this paper we describe the results of experiments using synchrotron radiation to trigger the Auger effect in living human cancer cells treated with a widely used chemotherapy drug: cis-diamminedichloroplatinum (II) (cisplatin). The experiments were carried out at the ID17 beamline of the European Synchrotron Radiation Facility, which produces a high-fluence monochromatic beam that is adjustable from 20 to 80 keV. Cisplatin was chosen as the carrier of platinum atoms in the cells because of its alkylating-like activity and the irradiation was done with monochromatic beams above and below the platinum K-shell edge (78.39 keV). Cell survival curves were comparable with those obtained for the same cells under conventional irradiation conditions. At a low dose of cisplatin (0.1 microM, 48 h), no difference was seen in survival when the cells were irradiated above and below the K-shell edge of platinum. Higher cisplatin concentrations were investigated to enhance the cellular platinum content. The results with 1 microM cisplatin for 12 h showed no difference when the cells were irradiated with beams above or below the platinum K-shell edge with the exception of the higher cell death resulting from drug toxicity. The intracellular content of platinum was significant, as measured macroscopically by inductively coupled plasma mass spectrometry. Its subcellular localization and particularly its presence in the cell nucleus were verified by microscopic synchrotron X-ray fluorescence. This was the first known attempt at K-shell edge photon activation of stable platinum in living cells with a platinum complex used for chemotherapy. Its evident toxicity in these cells leads us to put forth the hypothesis that cisplatin toxicity can mask the enhancement of cell death induced by the irradiation above the K-shell edge. However, K-shell edge photon activation of stable elements provides a powerful technique for the understanding of the biological effects of Auger processes. Further avenues of development are discussed.