Selenium preferentially accumulates in the eye lens following embryonic exposure: a confocal X-ray fluorescence imaging study.

Maternal transfer of elevated selenium (Se) to offspring is an important route of Se exposure for fish in the natural environment. However, there is a lack of information on the tissue specific spatial distribution and speciation of Se in the early developmental stages of fish, which provide important information about Se toxicokinetics. The effect of maternal transfer of Se was studied by feeding adult zebrafish a Se-elevated or a control diet followed by collection of larvae from both groups. Novel confocal synchrotron-based techniques were used to investigate Se within intact preserved larvae. Confocal X-ray fluorescence imaging was used to compare Se distributions within specific planes of an intact larva from each of the two groups. The elevated Se treatment showed substantially higher Se levels than the control; Se preferentially accumulated to highest levels in the eye lens, with lower levels in the retina, yolk and other tissues. Confocal X-ray absorption spectroscopy was used to determine that the speciation of Se within the eye lens of the intact larva was a selenomethionine-like species. Preferential accumulation of Se in the eye lens may suggest a direct cause-and-effect relationship between exposure to elevated Se and Se-induced ocular impairments reported previously. This study illustrates the effectiveness of confocal X-ray fluorescence methods for investigating trace element distribution and speciation in intact biological specimens.

Historical overview and new directions in bioarchaeological trace element analysis: a review.

Given their strong affinity for the skeleton, trace elements are often stored in bones and teeth long term. Diet, geography, health, disease, social status, activity, and occupation are some factors which may cause differential exposure to, and uptake of, trace elements, theoretically introducing variability in their concentrations and/or ratios in the skeleton. Trace element analysis of bioarchaeological remains has the potential, therefore, to provide rich insights into past human lifeways. This review provides a historical overview of bioarchaeological trace element analysis and comments on the current state of the discipline by highlighting approaches with growing momentum. Popularity for the discipline surged following preliminary studies in the 1960s to 1970s that demonstrated the utility of strontium (Sr) as a dietary indicator. During the 1980s, Sr/Ca ratio and multi-element studies were commonplace in bioarchaeology, linking trace elements with dietary phenomena. Interest in using trace elements for bioarchaeological inferences waned following a period of critiques in the late 1980s to 1990s that argued the discipline failed to account for diagenesis, simplified complex element uptake and regulation processes, and used several unsuitable elements for palaeodietary reconstruction (e.g. those under homeostatic regulation, those without a strong affinity for the skeleton). In the twenty-first century, trace element analyses have been primarily restricted to Sr and lead (Pb) isotope analysis and the study of toxic trace elements, though small pockets of bioarchaeology have continued to analyse multiple elements. Techniques such as micro-sampling, element mapping, and non-traditional stable isotope analysis have provided novel insights which hold the promise of helping to overcome limitations faced by the discipline. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s12520-020-01262-4.

Insights into biogenic and diagenetic lead exposure in experimentally altered modern and archaeological bone: Synchrotron radiation X-ray fluorescence imaging.

Bones represent a valuable biological archive of environmental lead (Pb) exposure for modern and archaeological populations. Synchrotron radiation X-ray fluorescence imaging (SR-XFI) generates maps of Pb in bone on a microstructural scale, potentially providing insights into an individual's history of Pb exposure and, in the context of archaeological bone, the biogenic or diagenetic nature of its uptake. The aims of this study were to (1) examine biogenic spatial patterns for Pb from bone samples of modern cadavers compared with patterns observed archaeologically, and (2) test the hypothesis that there are spatial differences in the distribution of Pb for diagenetic and biogenic modes of uptake in bone. To address these aims, this study used inductively coupled plasma-mass spectrometry (ICP-MS) and SR-XFI on unaltered and experimentally altered cadaveric bone samples (University of Saskatchewan, Saskatoon, SK) and archaeological bone samples from 18th to 19th century archaeological sites from Antigua and Lithuania. Bone concentrations of modern individuals are relatively low compared to those of archaeological individuals. SR-XFI results provide insights into modern Saskatchewan Pb exposure with some samples demonstrating a pattern of relatively low Pb exposure with higher levels of Pb exposure occurring in bone structures of a relatively older age that formed earlier in life, likely during the era of leaded gasoline (pre-1980s), and other samples demonstrating a pattern of fairly consistent, low-level exposure. Results support hypotheses for the spatial distribution of Pb corresponding to biogenic vs. diagenetic uptake. Diagenetic Pb is mainly confined to the periosteal surface of each sample with some enrichment of cracks and sub-periosteal canals. This may be useful in the future for differentiating diagenetic from biogenic Pb accumulation, analyzing environmental contamination, and informing sampling strategies in archaeological or fossil bone.

Recovery of Degraded-Beyond-Recognition 19th Century Daguerreotypes with Rapid High Dynamic Range Elemental X-ray Fluorescence Imaging of Mercury L Emission.

A daguerreotype image, the first commercialized photographic process, is composed of silver-mercury, and often silver-mercury-gold amalgam particles on the surface of a silver-coated copper plate. Specular and diffuse reflectance of light from these image particles produces the range of gray tones that typify these 19th century images. By mapping the mercury distribution with rapid-scanning, synchrotron-based micro-X-ray fluorescence (µ-XRF) imaging, full portraits, which to the naked eye are obscured entirely by extensive corrosion, can be retrieved in a non-invasive, non-contact, and non-destructive manner. This work furthers the chemical understanding regarding the production of these images and suggests that mercury is retained in the image particles despite surface degradation. Most importantly, µ-XRF imaging provides curators with an image recovery method for degraded daguerreotypes, even if the artifact's condition is beyond traditional conservation treatments.

Author Correction: Recovery of Degraded-Beyond-Recognition 19th Century Daguerreotypes with Rapid High Dynamic Range Elemental X-ray Fluorescence Imaging of Mercury L Emission.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Franklin expedition lead exposure: New insights from high resolution confocal x-ray fluorescence imaging of skeletal microstructure.

In the summer of 1845, under the command of Sir John Franklin, 128 officers and men aboard Royal Navy ships HMS Erebus and HMS Terror sailed into Lancaster Sound and entered the waters of Arctic North America. The goal of this expedition was to complete the discovery of a northwest passage by navigating the uncharted area between Barrow Strait and Simpson Strait. Franklin and his crew spent the first winter at Beechey Island, where three crewmen died and were buried. In September 1846, the ships became stranded in ice off the northwest coast of King William Island, where they remained until April 1848. At that time, the crew, reduced to 105, deserted the ships and retreated south along the island's western and southern shores in a desperate attempt to reach the mainland and via the Back River, to obtain aid at a Hudson's Bay Company Post. Sadly, not one individual survived. Previous analyses of bone, hair, and soft tissue samples from expedition remains found that crewmembers' tissues contained elevated lead (Pb) levels, suggesting that Pb poisoning may have contributed to their demise; however, questions remain regarding the timing and degree of exposure and, ultimately, the extent to which the crewmembers may have been impacted. To address this historical question, we investigated three hypotheses. First, if elevated Pb exposure was experienced by the crew during the expedition, we hypothesized that those sailors who survived longer (King William Island vs. Beechey Island) would exhibit more extensive uptake of Pb in their bones and vice versa. Second, we hypothesized that Pb would be elevated in bone microstructural features forming at or near the time of death compared with older tissue. Finally, if Pb exposure played a significant role in the failure of the expedition we hypothesized that bone samples would exhibit evidence of higher and more sustained uptake of Pb than that of a contemporary comparator naval population from the 19th century. To test these hypotheses, we analyzed bone and dental remains of crew members and compared them against samples derived from the Royal Navy cemetery in Antigua. Synchrotron-based high resolution confocal X-ray fluorescence imaging was employed to visualize Pb distribution within bone and tooth microstructures at the micro scale. The data did not support our first hypothesis as Pb distribution within the samples from the two different sites was similar. Evidence of Pb within skeletal microstructural features formed near the time of death lent support to our second hypothesis but consistent evidence of a marked elevation in Pb levels was lacking. Finally, the comparative analysis with the Antigua samples did not support the hypothesis that the Franklin sailors were exposed to an unusually high level of Pb for the time period. Taken all together our skeletal microstructural results do not support the conclusion that Pb played a pivotal role in the loss of Franklin and his crew.

Time-resolved X-ray excited optical luminescence from tris(2-phenyl pyridine)iridium [corrected].

Time-resolved X-ray Excited Optical Luminescence (TRXEOL) has been developed to investigate the optical properties of a green organometallic phosphor, tris(2-phenyl pyridine)iridium, Ir(ppy)3. Using time-gated measurements, we find that the characteristic luminescence band from a neat Ir(ppy)3 film is composed of a fast channel at approximately 534 nm and a slower channel at approximately 580 nm. The implication of this study and the applicability of the technique in the study of light emitting materials are noted.