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1.
Philos Trans A Math Phys Eng Sci ; 382(2273): 20230195, 2024 Jun 09.
Article in English | MEDLINE | ID: mdl-38736337

ABSTRACT

Micrometeorites are estimated to represent the main part of the present flux of extraterrestrial matter found on the Earth's surface and provide valuable samples to probe the interplanetary medium. Here, we describe large and representative collections of micrometeorites currently available to the scientific community. These include Antarctic collections from surface ice and snow, as well as glacial sediments from the eroded top of nunataks-summits outcropping from the icesheet-and moraines. Collections extracted from deep-sea sediments (DSS) produced a large number of micrometeorites, in particular, iron-rich cosmic spherules that are rarer in other collections. Collections from the old and stable surface of the Atacama Desert show that finding large numbers of micrometeorites is not restricted to polar regions or DSS. The advent of rooftop collections marks an important step into involving citizen science in the study of micrometeorites, as well as providing potential sampling locations over all latitudes to explore the modern flux. We explore their strengths of the collections to address specific scientific questions and their potential weaknesses. The future of micrometeorite research will involve the finding of large fossil micrometeorite collections and benefit from recent advances in sampling cosmic dust directly from the air. This article is part of the theme issue 'Dust in the Solar System and beyond'.

2.
Nat Clim Chang ; 14(4): 340-343, 2024.
Article in English | MEDLINE | ID: mdl-38617203

ABSTRACT

More than 60% of meteorite finds on Earth originate from Antarctica. Using a data-driven analysis that identifies meteorite-rich sites in Antarctica, we show climate warming causes many extraterrestrial rocks to be lost from the surface by melting into the ice sheet. At present, approximately 5,000 meteorites become inaccessible per year (versus ~1,000 finds per year) and, independent of the emissions scenario, ~24% will be lost by 2050, potentially rising to ∼76% by 2100 under a high-emissions scenario.

3.
PNAS Nexus ; 3(1): pgad414, 2024 Jan.
Article in English | MEDLINE | ID: mdl-38213614

ABSTRACT

Constraining the thermodynamic conditions within an impact structure during and after hypervelocity impacts is extremely challenging due to the transient thermal regimes. This work uses carbonate clumped-isotope thermometry to reconstruct absolute temperatures of impact lithologies within and close to the ∼66 Myr old Chicxulub crater (Yucatán, México). We present stable oxygen (δ18O), carbon (δ13C), and clumped-isotope (Δ47) data for carbonate-bearing impact breccias, impact melt rock, and target lithologies from four drill cores on a transect through the Chicxulub structure from the northern peak ring to the southern proximal ejecta blanket. Clumped isotope-derived temperatures (T(Δ47)) are consistently higher than maximum Late Cretaceous sea surface temperatures (35.5°C), except in the case of Paleogene limestones and melt-poor impact breccias outside of the crater, confirming the influence of burial diagenesis and a widespread and long-lived hydrothermal system. The melt-poor breccia unit outside the crater is overlain by melt-rich impact breccia yielding a much higher T(Δ47) of 111 ± 10°C (1 standard error [SE]), which likely traces the thermal processing of carbonate material during ejection. Finally, T(Δ47) up to 327 ± 33°C (1 SE) is determined for the lower suevite and impact melt rock intervals within the crater. The highest temperatures are related to distinct petrological features associated with decarbonation and rapid back-reaction, in which highly reactive CaO recombines with impact-released CO2 to form secondary CaCO3 phases. These observations have important climatic implications for the Cretaceous-Paleogene mass extinction event, as current numerical models likely overestimate the release of CO2 from the Chicxulub impact event.

4.
Talanta ; 263: 124714, 2023 Oct 01.
Article in English | MEDLINE | ID: mdl-37247458

ABSTRACT

Gallium is a moderately volatile, moderately siderophile element with two stable isotopes: 69Ga and 71Ga. A general interest in Ga isotopes arose over the last few years, as its moderately volatile behavior potentially marks it as a useful tracer of various processes such as condensation and evaporation. Nevertheless, there is a lack of agreement between laboratories for consistent δ71Ga values in geological reference materials. In this work, we have developed and evaluated two methods for purification protocols leading to precise analysis of gallium (Ga) isotopic composition in silicate rock materials. The first method is a three-step column chemistry using the resins AG1-X8, HDEHP, and AG50W-X12 whereas the second method uses only two columns, AG1-X8 and AG50W-X8. The two methods were applied to a range of both synthetic (multi-element) solutions and geological samples. Both methods show comparable results with no isotope fractionation occurring during purification chemistry, allowing us to define the δ71Ga of selected USGS reference materials (BHVO-2, BCR-2, RGM-2). Similar to previously reported results, we also observe no Ga fractionation between distinct igneous terrestrial materials.

5.
Anal Chim Acta ; 1240: 340744, 2023 Feb 01.
Article in English | MEDLINE | ID: mdl-36641153

ABSTRACT

Sulfur isotope ratios are often used as biogeochemical tracers to gain understanding of abiotic and biological processes involved in the sulfur cycle in both modern and ancient environments. There is however a lack of matrix-matched well-characterized isotopic reference materials that are essential for controlling the accuracy and precision. This study therefore focused on expanding and complementing the currently available sulfur isotope ratio data by providing the bulk sulfur isotopic composition, as determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), for a comprehensive set of commercially and/or readily available biological and geological reference materials. A total 7 isotopic reference materials and 41 elemental reference materials were studied. These reference materials include standards of terrestrial and marine animal origin, terrestrial plant origin, human origin, and geological origin. Different sample preparation protocols, including digestion and subsequent chromatographic isolation of S, were evaluated and the optimum approach selected for each matrix type. For achieving enhanced robustness, the sample preparation and sulfur isotope ratio measurements were done at two different laboratories for selected reference materials, while at one of the laboratories the measurements were additionally performed using two different MC-ICP-MS instruments. Determined δ34SVCDT and δ33SVCDT values compared well between the different laboratories, as well as between the different generation MC-ICP-MS instruments, and for standards that were previously characterized, our data are similar to literature values. The δ34SVCDT ranges determined for the different categories of the reference materials - terrestrial animal origin: +2 to +9‰, marine animal origin: +15 to +20‰, human origin: +6 to +10‰, terrestrial plant origin: -20 to +7‰, and geological origin: -12 to +21‰ - fit the expected values based on previous studies of similar types of matrices well. No significant mass-independent fractionation is observed when considering the expanded uncertainties for Δ33SV-CDT.


Subject(s)
Sulfur , Animals , Humans , Mass Spectrometry/methods , Sulfur Isotopes/analysis , Spectrum Analysis
6.
Sci Rep ; 12(1): 11376, 2022 07 05.
Article in English | MEDLINE | ID: mdl-35790847

ABSTRACT

To fully assess the resilience and recovery of life in response to the Cretaceous-Paleogene (K-Pg) boundary mass extinction ~ 66 million years ago, it is paramount to understand biodiversity prior to the Chicxulub impact event. The peak ring of the Chicxulub impact structure offshore the Yucatán Peninsula (México) was recently drilled and extracted a ~ 100 m thick impact-generated, melt-bearing, polymict breccia (crater suevite), which preserved carbonate clasts with common biogenic structures. We pieced this information to reproduce for the first time the macrobenthic tracemaker community and marine paleoenvironment prior to a large impact event at the crater area by combining paleoichnology with micropaleontology. A variable macrobenthic tracemaker community was present prior to the impact (Cenomanian-Maastrichtian), which included soft bodied organisms such as annelids, crustaceans and bivalves, mainly colonizing softgrounds in marine oxygenated, nutrient rich, conditions. Trace fossil assemblage from these upper Cretaceous core lithologies, with dominant Planolites and frequent Chondrites, corresponds well with that in the overlying post-impact Paleogene sediments. This reveals that the K-Pg impact event had no significant effects (i.e., extinction) on the composition of the macroinvertebrate tracemaker community in the Chicxulub region.


Subject(s)
Extinction, Biological , Meteoroids , Biodiversity , Fossils , Mexico
7.
Sci Rep ; 12(1): 9280, 2022 06 03.
Article in English | MEDLINE | ID: mdl-35660749

ABSTRACT

The high temperatures reached during cremation lead to the destruction of organic matter preventing the use of traditional isotopic methods for dietary reconstructions. Still, strontium isotope (87Sr/86Sr) and concentration ([Sr]) analyses of cremated human remains offer a novel way to assess changing consumption patterns in past populations that practiced cremation, as evidenced by a large amount of new data obtained from Metal Ages and Gallo-Roman human remains from Destelbergen, Belgium. The Gallo-Roman results show significantly higher [Sr] and a narrower interquartile range in 87Sr/86Sr (0.7093-0.7095), close to the value of modern-day seawater (0.7092). This contrasts with the Metal Ages results, which display lower concentrations and a wider range in 87Sr/86Sr (0.7094-0.7098). This typical Sr signature is also reflected in other sites and is most likely related to an introduction of marine Sr in the form of salt as a food preservative (e.g. salt-rich preserved meat, fish and fish sauce). Paradoxically, this study highlights caution is needed when using 87Sr/86Sr for palaeomobility studies in populations with high salt consumption.


Subject(s)
Cremation , Strontium Isotopes , Animals , Body Remains , Bone and Bones/chemistry , Diet , Isotopes/analysis , Strontium/analysis , Strontium Isotopes/analysis
8.
Sci Adv ; 8(4): eabj8138, 2022 Jan 28.
Article in English | MEDLINE | ID: mdl-35080966

ABSTRACT

Meteorites provide a unique view into the origin and evolution of the Solar System. Antarctica is the most productive region for recovering meteorites, where these extraterrestrial rocks concentrate at meteorite stranding zones. To date, meteorite-bearing blue ice areas are mostly identified by serendipity and through costly reconnaissance missions. Here, we identify meteorite-rich areas by combining state-of-the-art datasets in a machine learning algorithm and provide continent-wide estimates of the probability to find meteorites at any given location. The resulting set of ca. 600 meteorite stranding zones, with an estimated accuracy of over 80%, reveals the existence of unexplored zones, some of which are located close to research stations. Our analyses suggest that less than 15% of all meteorites at the surface of the Antarctic ice sheet have been recovered to date. The data-driven approach will greatly facilitate the quest to collect the remaining meteorites in a coordinated and cost-effective manner.

9.
Sci Total Environ ; 808: 152059, 2022 Feb 20.
Article in English | MEDLINE | ID: mdl-34863743

ABSTRACT

Due to the straightforward and non-invasive sampling, ease of transport and long-term storage and access to time-resolved information, determination of element concentrations and isotope ratios in hair and nails finds increasing use. Multi-isotopic information preserved in keratinous tissues allows one to reveal dietary, physiological and environmental influences, but progress in this area is still limited by complicated and time-consuming analytical procedures and challenges in accuracy assessment. In this study, longitudinal distributions of δ34S, 87Sr/86Sr, 207,208Pb/206Pb, δ66Zn, δ56Fe, δ65Cu, δ26Mg, and δ114Cd were obtained for hair and nails collected from nine subjects with different age, biological sex, diet and/or place of residence. For S and Zn, the distribution along hair strands revealed a trend towards a heavier isotopic signature from the proximal to the distal end, with a maximum difference within the hair of a single subject of 1.2‰ (Δ34S) and 0.4‰ (Δ66Zn). For Fe, Cu, Mg and Cd, a shift towards either a lighter (Cu) or heavier (Fe, Mg and Cd) isotopic composition is accompanied by increasing concentration towards the distal hair end, indicating possible isotope fractionation during deposition or external contamination with a different isotopic composition. Pb and Sr isotope ratios are relatively stable throughout the hair strands despite notable concentration increases towards the distal end, likely reflecting external contamination. The isotopic composition of Sr points to tap water as a probable main source, explaining the relative stability of the ratio for individuals from the same geographical location. For Pb, isotopic compositions suggest tap water and/or indoor dust as possible sources. Similar δ34S, 87Sr/86Sr, 207,208Pb/206Pb, δ66Zn, δ56Fe, and δ65Cu observed for hair, fingernails and toenails sampled from the same individual suggest that keratinous tissues are conservative receivers of internal and external inputs and can be used complementary. Seasonal variation in δ34S, 207,208Pb/206Pb, and δ65Cu was observed for fingernails.


Subject(s)
Isotopes , Nails , Dust , Hair , Humans , Keratins
10.
PLoS One ; 16(8): e0254760, 2021.
Article in English | MEDLINE | ID: mdl-34347802

ABSTRACT

Little is known of the properties of the sarsen stones (or silcretes) that comprise the main architecture of Stonehenge. The only studies of rock struck from the monument date from the 19th century, while 20th century investigations have focussed on excavated debris without demonstrating a link to specific megaliths. Here, we present the first comprehensive analysis of sarsen samples taken directly from a Stonehenge megalith (Stone 58, in the centrally placed trilithon horseshoe). We apply state-of-the-art petrographic, mineralogical and geochemical techniques to two cores drilled from the stone during conservation work in 1958. Petrographic analyses demonstrate that Stone 58 is a highly indurated, grain-supported, structureless and texturally mature groundwater silcrete, comprising fine-to-medium grained quartz sand cemented by optically-continuous syntaxial quartz overgrowths. In addition to detrital quartz, trace quantities of silica-rich rock fragments, Fe-oxides/hydroxides and other minerals are present. Cathodoluminescence analyses show that the quartz cement developed as an initial <10 µm thick zone of non-luminescing quartz followed by ~16 separate quartz cement growth zones. Late-stage Fe-oxides/hydroxides and Ti-oxides line and/or infill some pores. Automated mineralogical analyses indicate that the sarsen preserves 7.2 to 9.2 area % porosity as a moderately-connected intergranular network. Geochemical data show that the sarsen is chemically pure, comprising 99.7 wt. % SiO2. The major and trace element chemistry is highly consistent within the stone, with the only magnitude variations being observed in Fe content. Non-quartz accessory minerals within the silcrete host sediments impart a trace element signature distinct from standard sedimentary and other crustal materials. 143Nd/144Nd isotope analyses suggest that these host sediments were likely derived from eroded Mesozoic rocks, and that these Mesozoic rocks incorporated much older Mesoproterozoic material. The chemistry of Stone 58 has been identified recently as representative of 50 of the 52 remaining sarsens at Stonehenge. These results are therefore representative of the main stone type used to build what is arguably the most important Late Neolithic monument in Europe.


Subject(s)
Geologic Sediments/chemistry , Automation , Calibration , England , Hyperspectral Imaging , Image Processing, Computer-Assisted , Isotopes/analysis , Minerals/analysis , Optical Imaging , Spectrometry, X-Ray Emission , Spectrophotometry, Atomic , Tomography, X-Ray Computed , Trace Elements/analysis
11.
Front Microbiol ; 12: 668240, 2021.
Article in English | MEDLINE | ID: mdl-34248877

ABSTRACT

We report on the effect of the end-Cretaceous impact event on the present-day deep microbial biosphere at the impact site. IODP-ICDP Expedition 364 drilled into the peak ring of the Chicxulub crater, México, allowing us to investigate the microbial communities within this structure. Increased cell biomass was found in the impact suevite, which was deposited within the first few hours of the Cenozoic, demonstrating that the impact produced a new lithological horizon that caused a long-term improvement in deep subsurface colonization potential. In the biologically impoverished granitic rocks, we observed increased cell abundances at impact-induced geological interfaces, that can be attributed to the nutritionally diverse substrates and/or elevated fluid flow. 16S rRNA gene amplicon sequencing revealed taxonomically distinct microbial communities in each crater lithology. These observations show that the impact caused geological deformation that continues to shape the deep subsurface biosphere at Chicxulub in the present day.

12.
Sci Adv ; 7(9)2021 Feb.
Article in English | MEDLINE | ID: mdl-33627429

ABSTRACT

The Cretaceous-Paleogene (K-Pg) mass extinction is marked globally by elevated concentrations of iridium, emplaced by a hypervelocity impact event 66 million years ago. Here, we report new data from four independent laboratories that reveal a positive iridium anomaly within the peak-ring sequence of the Chicxulub impact structure, in drill core recovered by IODP-ICDP Expedition 364. The highest concentration of ultrafine meteoritic matter occurs in the post-impact sediments that cover the crater peak ring, just below the lowermost Danian pelagic limestone. Within years to decades after the impact event, this part of the Chicxulub impact basin returned to a relatively low-energy depositional environment, recording in unprecedented detail the recovery of life during the succeeding millennia. The iridium layer provides a key temporal horizon precisely linking Chicxulub to K-Pg boundary sections worldwide.

13.
Anal Chem ; 92(5): 3572-3580, 2020 Mar 03.
Article in English | MEDLINE | ID: mdl-32013393

ABSTRACT

This work evaluates the use of nanosecond laser ablation-multicollector inductively coupled plasma-mass spectrometry (ns-LA-MC-ICP-MS) for Fe isotopic analysis of glassy cosmic spherules. Several protocols for data acquisition from the transient signals were compared, with the integration method, i.e., isotope ratios obtained by dividing the corresponding signal intensities integrated over the selected signal segment, providing the best precision. The bias caused by instrumental mass discrimination was corrected for by a combination of internal correction using Ni as an internal standard (coming from a conebulized standard solution) and external correction using a matrix-matched standard. Laser spot size and repetition rate were adapted to match the signal intensities for sample and standard within ±10%. For in situ isotopic analysis, the precision of the δ56Fe values ranged between 0.02 and 0.11‰ (1 SD, based on 4 measurement sessions, each based on ablation along 5 lines for 30 s each) and 0.03-0.17‰ (SD, based on 3 measurement sessions) for glass reference materials and micrometeorites, respectively. Despite this excellent reproducibility, the variation of the isotope ratios along a single ablation line indicated isotopic inhomogeneity exceeding 1‰ in some micrometeorites. Isotopic analysis via pneumatic nebulization MC-ICP-MS, after sample digestion and chromatographic Fe isolation, was performed to validate the results obtained by in situ isotopic analysis, and good agreement was achieved between the δ-values obtained via both approaches and with those reported in literature for MPI-DING and USGS glass reference materials. Also for the glassy cosmic spherules, overall, there was a good match between the ns-LA-MC-ICP-MS and solution MC-ICP-MS results.

14.
J Synchrotron Radiat ; 26(Pt 6): 2033-2039, 2019 Nov 01.
Article in English | MEDLINE | ID: mdl-31721748

ABSTRACT

At the French synchrotron facility SOLEIL, a new X-ray imaging facility PUMA (Photons Utilisés pour les Matériaux Anciens) has been made available to scientific communities studying materials from cultural heritage. This new instrument aims to achieve 2D and 3D imaging with microscopic resolution, applying different analytical techniques including X-ray fluorescence spectroscopy (XRF), X-ray absorption spectroscopy (XAS), X-ray diffraction and phase-contrast imaging. In order to discover its capabilities a detailed analytical characterization of this beamline as an analytical and imaging tool is deemed necessary. In this work, (confocal) XRF and XAS analyses are demonstrated using the Seymchan pallasite meteorite and an Antarctic unmelted micrometeorite as case studies. The obtained spatial resolution (2 µm × 3 µm) and sensitivity (detection limits <10 p.p.m. for 1 s acquisition at 18 keV) show that PUMA is a competitive state-of-the-art beamline, providing several high-profile and high-in-demand analytical methods while maintaining applicability towards a wide range of heritage-oriented sciences.

15.
Sci Adv ; 5(9): eaax4184, 2019 09.
Article in English | MEDLINE | ID: mdl-31555741

ABSTRACT

The breakup of the L-chondrite parent body in the asteroid belt 466 million years (Ma) ago still delivers almost a third of all meteorites falling on Earth. Our new extraterrestrial chromite and 3He data for Ordovician sediments show that the breakup took place just at the onset of a major, eustatic sea level fall previously attributed to an Ordovician ice age. Shortly after the breakup, the flux to Earth of the most fine-grained, extraterrestrial material increased by three to four orders of magnitude. In the present stratosphere, extraterrestrial dust represents 1% of all the dust and has no climatic significance. Extraordinary amounts of dust in the entire inner solar system during >2 Ma following the L-chondrite breakup cooled Earth and triggered Ordovician icehouse conditions, sea level fall, and major faunal turnovers related to the Great Ordovician Biodiversification Event.

16.
Proc Natl Acad Sci U S A ; 116(39): 19342-19351, 2019 09 24.
Article in English | MEDLINE | ID: mdl-31501350

ABSTRACT

Highly expanded Cretaceous-Paleogene (K-Pg) boundary section from the Chicxulub peak ring, recovered by International Ocean Discovery Program (IODP)-International Continental Scientific Drilling Program (ICDP) Expedition 364, provides an unprecedented window into the immediate aftermath of the impact. Site M0077 includes ∼130 m of impact melt rock and suevite deposited the first day of the Cenozoic covered by <1 m of micrite-rich carbonate deposited over subsequent weeks to years. We present an interpreted series of events based on analyses of these drill cores. Within minutes of the impact, centrally uplifted basement rock collapsed outward to form a peak ring capped in melt rock. Within tens of minutes, the peak ring was covered in ∼40 m of brecciated impact melt rock and coarse-grained suevite, including clasts possibly generated by melt-water interactions during ocean resurge. Within an hour, resurge crested the peak ring, depositing a 10-m-thick layer of suevite with increased particle roundness and sorting. Within hours, the full resurge deposit formed through settling and seiches, resulting in an 80-m-thick fining-upward, sorted suevite in the flooded crater. Within a day, the reflected rim-wave tsunami reached the crater, depositing a cross-bedded sand-to-fine gravel layer enriched in polycyclic aromatic hydrocarbons overlain by charcoal fragments. Generation of a deep crater open to the ocean allowed rapid flooding and sediment accumulation rates among the highest known in the geologic record. The high-resolution section provides insight into the impact environmental effects, including charcoal as evidence for impact-induced wildfires and a paucity of sulfur-rich evaporites from the target supporting rapid global cooling and darkness as extinction mechanisms.

17.
ACS Appl Mater Interfaces ; 11(14): 13694-13703, 2019 Apr 10.
Article in English | MEDLINE | ID: mdl-30896141

ABSTRACT

Shaping metal-organic frameworks (MOFs) into robust particles with a controllable size is of large interest to the field of adsorption. Therefore, a method is presented here to produce robust MOF beads of different sizes, ranging from 250 µm to several millimeters, which, moreover, preserve the adsorption properties of the unformulated MOF. A simple, mild, and flexible method is demonstrated with the zeolitic imidazolate framework-8 (ZIF-8)/polyvinyl formal composite material. The properties of the composite material are determined via optical imaging, scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma mass spectrometry, X-ray diffraction, mercury intrusion, argon porosimetry and pycnometry as well as thermogravimetric analysis/differential scanning calorimetry, crush strength tests, and immersion experiments. The proposed method allows the production of resistant particles with a high MOF loading (up to 85 wt %) and remarkable structural and textural properties required for adsorptive separation processes, including a preserved ZIF-8 crystalline structure, microporosity, and a narrow macropore size distribution (1.27 µm average). The particles show a spherical shape with an average aspect ratio of 0.85. The stability tests demonstrated that the composite MOF material exhibits a high mechanical strength (3.09 N/Pc crushing strength) almost equivalent to that of a widely used commercial zeolite material. Furthermore, the material remains stable up to 200 °C and in most solvents. The adsorption properties are explored via static and dynamic experiments in the vapor and liquid phases. The results show that the adsorption capacities are only reduced in proportion to the binder content compared with the pristine material, indicating no binder intrusion in the ZIF-8 pores. Fixed-bed experiments demonstrate the remarkable separation performance in the vapor phase, whereas mass transfer limitations arise in the liquid phase with increasing flow rate. The mass transfer limitations are attributed to the diffusion in the macropores or through the ZIF-8 crystal outer layer.

18.
Sci Rep ; 8(1): 10790, 2018 Aug 02.
Article in English | MEDLINE | ID: mdl-30072719

ABSTRACT

Cremated human remains from Stonehenge provide direct evidence on the life of those few select individuals buried at this iconic Neolithic monument. The practice of cremation has, however, precluded the application of strontium isotope analysis of tooth enamel as the standard chemical approach to study their origin. New developments in strontium isotopic analysis of cremated bone reveal that at least 10 of the 25 cremated individuals analysed did not spend their lives on the Wessex chalk on which the monument is found. Combined with the archaeological evidence, we suggest that their most plausible origin lies in west Wales, the source of the bluestones erected in the early stage of the monument's construction. These results emphasise the importance of inter-regional connections involving the movement of both materials and people in the construction and use of Stonehenge.


Subject(s)
Anthropology, Physical/methods , Archaeology/methods , Body Remains/chemistry , Dental Enamel/chemistry , Strontium Isotopes/chemistry , Cremation , Human Migration , Humans , Mass Spectrometry , Wales
19.
Angew Chem Int Ed Engl ; 57(20): 5660-5664, 2018 05 14.
Article in English | MEDLINE | ID: mdl-29570239

ABSTRACT

An efficient metal-free cascade reaction between 1-dibromovinyl-2-nitro-substituted arenes and secondary amines results in the formation of polycyclic pseudoindoxyls in a single step. The reaction mechanism leading to these fused ring systems was investigated, and is believed to involve the initial formation of nitroarylated ynamines/ynamides. These intermediates cycloisomerize towards N-alkenyl-tethered 2-aminoisatogens via a carbene intermediate as demonstrated by QTAIM (quantum theory of atoms in molecules) and ELF (electron localization function) analysis. A subsequent intramolecular dipolar cycloaddition afforded the title compounds.

20.
Am J Phys Anthropol ; 160(3): 397-413, 2016 07.
Article in English | MEDLINE | ID: mdl-27061584

ABSTRACT

OBJECTIVES: As many individuals were cremated in Neolithic and Bronze Age Ireland, they have not featured in investigations of individual mobility using strontium isotope analysis. Here, we build on recent experiments demonstrating excellent preservation of biogenic (87) Sr/(86) Sr in calcined bone to explore mobility in prehistoric Northern Ireland. MATERIALS AND METHODS: A novel method of strontium isotope analysis is applied to calcined bone alongside measurements on tooth enamel to human remains from five Neolithic and Bronze Age sites in Northern Ireland. We systematically sampled modern vegetation around each site to characterize biologically available strontium, and from this calculated expected values for humans consuming foods taken from within 1, 5, 10 and 20 Km catchments. This provides a more nuanced way of assessing human use of the landscape and mobility than the 'local' vs. 'non-local' dichotomy that is often employed. RESULTS: The results of this study 1) provide further support for the reliability of strontium isotope analysis on calcined bone, and 2) demonstrate that it is possible to identify isotopic differences between individuals buried at the same site, with some consuming food grown locally (within 1-5 Km) while others clearly consumed food from up to 50 Km away from their burial place. DISCUSSION: Hints of patterning emerge in spite of small sample numbers. At Ballynahatty, for instance, those represented by unburnt remains appear to have consumed food growing locally, while those represented by cremated remains did not. Furthermore, it appears that some individuals from Ballynahatty, Annaghmare and Clontygora either moved in the last few years of their life or their cremated remains were brought to the site. These results offer new insights into the choice behind coterminous cremation and inhumation rites in the Neolithic. Am J Phys Anthropol 160:397-413, 2016. © 2016 Wiley Periodicals, Inc.


Subject(s)
Bone and Bones/chemistry , Burial/history , Cremation/history , Strontium Isotopes/analysis , Transportation/history , Anthropology, Physical , History, Ancient , Humans , Northern Ireland , Tooth/chemistry
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