This paper explores early broomcorn millet (hereafter millet) cultivation in Greece during the Bronze Age. The primary archaeobotanical data for this study derive from the site of Skala Sotiros on the island of Thasos in northern Greece. The site provides unique insights into localized Bronze Age agricultural practices, revealing both divergence from southern Greece agricultural systems and potential influences from exchange networks that linked northern Greece to the southern Balkans and the Pontic steppe-Black Sea region. Systematic sampling of the Bronze Age layers at Skala Sotiros has yielded a diverse assemblage with a notable abundance of millet (Panicum miliaceum), a crop almost absent from contemporary southern Greece. Recent radiocarbon dates on millet grains from Skala Sotiros contribute new evidence toward understanding the routes through which millet could have been introduced into the region during the Bronze Age. This study explores the interplay of environmental and cultural factors in the dispersal of millet in Greece, considering environmental stress, cultural dynamics, population movements, and interaction networks. The extensive review of archaeobotanical data across Greece demonstrates how the cultivation of millet may have served as a culinary identity signifier, providing further evidence of differences between northern and southern Greece.
Bread is a fundamental foodstuff that has driven social and technological development for millennia, with the earliest evidence dating to pre-agricultural societies. While archaeological sites from the Neolithic period show systematic grain processing, well-preserved bread from the subsequent Early Bronze Age, particularly in a clear ritual context, is exceedingly rare. Here we report the discovery and comprehensive archaeometric analysis; employing Scanning Electron Microscopy (SEM) coupled with Energy Dispersive X-ray (EDX) spectroscopy, Vibrational Spectroscopy (FTIR and Raman), and Thermal Analysis (TGA-DSC) of a 5,000-year-old carbonized bread from the Küllüoba settlement in Anatolia, dated 3200-3000 BC. Microscopic examinations reveal that it is made from coarsely ground emmer wheat (Triticum dicoccum) and a small amount of lentils (Lens culinaris). The presence of air voids suggests kneaded dough, possibly leavened. The detection of rachis fragments indicates the use of unsieved flour. Intentionally deposited and subsequently carbonized, the bread was sealed beneath a layer of sterile soil and appears to have been an offering connected with the ritual abandonment of the structure. This finding offers unique evidence of advanced food technology and highlights the symbolic importance of bread in Early Bronze Age societies, directly linking food production to cultural and ritual practices.
Strontium isotope analysis is now a key method for investigating ancient human mobility, leading to a rapid expansion of available ⁸⁷Sr/⁸⁶Sr datasets. Owing to the relatively homogeneous surface geological conditions across present-day Denmark (excluding Bornholm) and the growing number of regional datasets, it is now possible to construct statistically defined ranges of bioavailable strontium directly from archaeological human data. In this study, we compile 513 published strontium isotope values from tooth enamel and pars petrosa of individuals recovered from archaeological sites across present-day Denmark and add 115 new values. Using the Median Absolute Deviation (MAD) method to identify outliers in this comprehensive and diachronic database of 628 human ⁸⁷Sr/⁸⁶Sr ratios, we define the first statistically constrained, human-based range of bioavailable strontium isotope values for Denmark to ⁸⁷Sr/⁸⁶Sr = 0.7089-0.7117. We interpret this range as representing typical bioavailable strontium signatures in prehistoric Denmark. We then apply it, for the first time, as one of the reference frameworks for investigating the mobility of non-elite individuals from the Nordic Bronze Age in present-day Denmark. In total, we conducted 34 strontium isotope analyses on individuals from two sites: fourteen analyses from six inhumations at Kalvehavegård on Funen, and twenty analyses from cremated individuals at Sølager on Zealand. We compare the individuals' strontium isotope values both to established baselines relevant for past mobility studies and to the new human-based range defined in this study. The results indicate that mobility during the Nordic Bronze Age was not restricted to elite social groups but also encompassed some non-elite individuals, offering new insights into social dynamics during this formative period of European prehistory. Moreover, the new strontium dataset presented here represents the first accessible, country-wide compilation of human-derived Sr data for Denmark, providing a robust platform for future comparative studies and mobility research in the region.
The removal of active corrosion layers from bronze heritage objects is a critical conservation challenge, requiring methods that balance cleaning efficiency with surface preservation and environmental sustainability. Traditional chemical treatments often rely on chelating agents loaded into hydrogels, which can pose risks of uncontrolled diffusion and residue retention. This study presents a biobased, chelator-free alternative using cellulose nanofibril (CNF) hydrogels cross-linked with glycine whose use in conservation of cultural heritage is new. Unlike conventional systems, these physically cross-linked supramolecular hydrogels utilize the amphoteric properties of natural amino acids to sequester copper corrosion products via a coordination-driven mechanism, eliminating the need for adding complexing agents. We synthesized and characterized a series of hydrogel formulations. Mechanical compressive testing and water retention allowed to identify the right formulation offering a high-water content (96.3%), superior elastic recovery, and excellent conformability to complex 3D surfaces compared to traditional agar-EDTA hydrogels. The cleaning performance was evaluated against the traditional agar-EDTA alternative on artificially patinated bronze coupons, as well as a complex 3D model sculpture. A non-invasive multimodal imaging approach combining Raman spectroscopy, Hyperspectral Imaging in the SWIR, and quantitative micro Energy Dispersive X-Ray Fluorescence spectrometry revealed that the chelator-free nanocellulose hydrogels achieved a more uniform and effective removal of sulfated and chlorinated corrosion products than the agar-EDTA hydrogel. Infrared spectroscopy further confirmed the coordination of extracted Cu (II) ions within the porous nanostructure of the new hydrogel. Finally, a life cycle assessment (LCA) was conducted to quantify the environmental impacts, identifying production hotspots, with sensitivity analyses pointing toward strategies for future improvement.
The Late Bronze Age (ca. 1300-800 BCE) of Central Europe is often characterised as a period of increasing mobility, socioeconomic transformation, environmental fluctuations, and expanding cultural networks. However, reconstructing the demographic aspects of these changes has been hindered by cremation being the dominant mortuary practice, limiting biomolecular approaches. Here, we integrate ancient DNA, oxygen and strontium isotope analyses, and osteoarchaeology to examine rare inhumation burials from Kuckenburg and Esperstedt in Central Germany (n = 36) and compare them to contemporaneous inhumations from the neighbouring regions of South Germany, Bohemia (Czechia) and Southwest/Central Poland (n = 33). Genome-wide data show genetic continuity with preceding Early Bronze Age populations, alongside gradual increases in Early European Farmer-related ancestry, albeit with regionally different timing and extent, reflecting a nuanced pattern of mobility and admixture. Oxygen and strontium isotope data from Central Germany indicate that most individuals match the local isotope signal, including those who were cremated or had a different diet, and with only a few isotopic outliers, suggesting that mobility was present but not extensive. Overall, our findings suggest that the diverse inhumation practices at Kuckenburg and Esperstedt were culturally motivated, reflecting local traditions and ongoing regional interconnectedness rather than the influx of new genetic groups or non-local individuals.
The transition from the latter part of the Early (Umm an-Nar: 2700-2000 bce) to Middle (Wadi Suq: 2000-1600 bce) Bronze Age in southeastern Arabia was once interpreted as a time of sociopolitical and economic collapse in the face of climate change. However, recent archaeological and bioarchaeological studies have demonstrated gradual and more nuanced adaptation in response to environmental challenges. The site of Shimal in the Emirate of Ras Al Khaimah, UAE is uniquely suited to expanding our understanding of this transition because-unlike most Umm an-Nar sites, which were abandoned by ca. 2000 bce-Shimal was continuously occupied throughout the third and second millennia. Strontium, oxygen, and carbon isotopes in human teeth (n = 57 teeth from 50 individuals) from two Umm an-Nar and four Wadi Suq tombs were analyzed to investigate shifting forms of social organization. Strontium isotope ratios differed statistically over time, although only a slight increase was evident in the Wadi Suq. Stable oxygen isotope values varied significantly between the earlier Umm an-Nar tomb Unar 1 and all later tombs. Stable carbon isotope values remained consistent throughout both periods. Continuity in the region is evident, reflective of the unique geographic location of Shimal as an oasis whose water resources enabled the community to better withstand the effects of aridification and to maintain subsistence strategies. At the same time, however, temporal shifts in strontium and oxygen isotopes may point to the presence of people who migrated north in search of environmental stability.
Dielectric energy storage capacitors have attracted considerable attention due to their excellent performance. Tungsten bronze-type ceramics have long been underestimated for energy storage applications owing to their relatively low breakdown strength and polarization. In this work, a lead-free relaxor ferroelectric ceramic, BaSrTiNb2-xTaxO9, was developed through Ta doping. Under an applied electric field, the material achieves a high recoverable energy density of 9.5 J/cm3 with an efficiency of 87.8%. Notably, it also exhibits excellent thermal stability and ultrafast discharge characteristics. The optimization strategy proposed in this study offers valuable guidance for the development of high-performance dielectric energy storage ceramics. It points to a direction for designing materials that combine superior energy storage properties with good temperature stability and provides an important reference for promoting technological innovation in advanced ceramic-based energy storage devices such as multilayer ceramic capacitors (MLCCs). It is expected to lead the development of the next generation of high-temperature stable dielectric materials.
An X-ray Absorption Spectroscopy (XAS) and Electron Paramagnetic Resonance (EPR) investigation of protohistoric blue vitreous materials was undertaken, aimed at ascertaining the valence state speciation of Cu and Co, suspected to play a role in the colour origin. Five different glass artefacts coming from Paduli (Colli sul Velino, Rieti, Italy) were investigated. A bichrome blue and white vessel fragment represents the only Natron glass. The other four beads, instead, are LMHK glass. A relevant question deals with concentration, distribution, and valence states of the transition elements Cu and Co. Two out of the five colored objects, in fact, contain only Cu, whilst the others exhibit both Cu and Co. A sample holder was specifically designed to ensure minimal invasiveness during XAS measurements. Multiple measurements (up to six) were performed for each sample at the Cu and/or Co edges to verify sample homogeneity. Fragments of the samples, when available, were investigated by EPR without manipulation to further characterize the CuII aliquot in the materials. The XAS spectra provided significant information confirming the presence of the CoII chromophore in the samples where this species is chemically more abundant, and identifying and quantifying the presence of the CuII chromophore. CuII, as revealed by EPR, appears in a distorted (4 + 2)-fold coordination and partly clustered to form pairs. This spectroscopic approach, combining XAS and EPR techniques, proves to be successful in the characterization of Co- and Cu-based blue colors in the glasses of the Bronze Age, highlighting the high skill reached in the production.
In Late Bronze Age Sardinia, Italy (ca. 1350-1200 BC), communities constructed distinctive stone structures centered on vertical shafts intersecting the groundwater table or monumentalized natural springs. Conventionally termed pozzi sacri ("sacred wells") or "well temples" in archeological literature, approximately 66 sites containing 75 monuments have been documented. Included on Italy's Tentative List for UNESCO World Heritage nomination, these monuments have attracted considerable public interest and continue to draw visitors from around the world. These structures feature elaborate masonry, descending staircases, and ritual deposits, yet their design appears poorly optimized for water collection which is significantly different from sacred wells elsewhere in the world. This note examines the physical dimensions of these monuments, highlighting that although excavation depths vary, with some extending significantly below the water table, chambers were designed to accommodate shallow water accumulation rather than deep storage. Using Santa Cristina, Cuccuru Nuraxi, and Su Tempiesu-Orune as case studies, the analysis demonstrates that paved chamber floors and design choices distinguishing these structures from utilitarian wells are consistent across the inventory. While the term "well" implies water extraction, the archeological evidence suggests groundwater may have been conceptualized as a subterranean boundary rather than a primary resource target.
Interfacial engineering offers a powerful route to enhance ion transport and electron mobility in lithium-ion batteries (LIBs) through the induction of built-in electric fields (BIEFs) at the interface, which in turn facilitates faster Li+ diffusion. Yet, direct experimental validation of this concept in intercalation-type materials has not been investigated. In this work, bronze titanium oxide (TiO2 (B)) is strategically integrated with expanded graphite (EG), producing a strong interfacial BIEF driven by their distinct work functions, as confirmed by Kelvin probe force microscopy (KPFM). As a result, the TiO2 (B)/EG electrode delivers a specific capacity of 75 mAh g-1 at 10 A g-1 along with 70% capacity retention after 1000 cycles at 2 A g-1. Galvanostatic intermittent titration (GITT) and electrochemical impedance spectroscopy (EIS) measurements substantiate the reduction in charge-transfer resistance accompanied by enhanced Li+ diffusion. Density functional theory (DFT) calculations further verify the presence of the BIEF and clarify its role in lowering Li+ insertion/extraction energy barriers, thereby enabling highly reversible and stable high-rate operation. Overall, this study demonstrates that BIEF modulation can effectively address the intrinsic kinetic limitations of intercalation-type materials, offering a viable strategy for the development of next-generation high-power, fast-charging lithium-ion battery anodes.
Ion implantation is introduced as a novel and controllable approach to incorporate hydrogen into α-MoO3 crystals and induce the formation of hydrogen molybdenum bronze phases (HxMoO3) below the implanted layer. By tuning the ion fluence, this technique enables precise defect engineering and phase transformation, offering a versatile and reproducible strategy for tailoring the material functional properties. High-resolution X-ray diffraction (HRXRD) reveals a gradual expansion of the b lattice parameter for fluences up to 1 × 1017 cm-2, attributed to defect-induced lattice distortion. For higher fluences, instead of typical strain saturation, a new diffraction peak emerges, revealing the formation of type-I HxMoO3, as also confirmed by Raman spectroscopy. This phase forms below the implanted layer and extends up to ∼1 µm into the material, as confirmed by transmission electron microscopy (TEM). This phase transformation demonstrates reversibility, with the HxMoO3 signature disappearing upon air annealing at 300°C. HRXRD curve fitting enables assessment of strain/damage profiles evolution with fluence, providing insight into the defect creation and accumulation mechanisms. These structural and compositional changes are accompanied by a quasi-linear increase of electrical conductivity with fluence, by several orders of magnitude, attributed to the presence of HxMoO3 phases, extended defects, and new suboxide minority phases.
Metal corrosion has caused huge economic losses and security risks. Thus, fast and simple detection of metal corrosion are in high demand. Herein, strong yellow fluorescence covalent organic frameworks (Tma-Dmh-COF) with superior response to copper ions (Cu2+) was synthesized by 2,4, 6-trimethoxy-homophentriformaldehyde (Tma) and 2, 5-dimethoxy-p-phenylhydrazide (Dmh). On this basis, a sensitive and rapid fluorescent sensor for Cu2+ detection was proposed with the detection limit of 72 nmol L-1. The fluorescence quenching effect of Tma-Dmh-COF was attributed to the strong coordination between the O,N,O'-chelating site in the pore wall of Tma-Dmh-COF and Cu2+. Moreover, using Tma-Dmh-COF as signal probe and silicon quantum dots (SiQDs) as reference probe, a ratiometric fluorescent sensor for Cu2+ was designed and successfully applied for monitoring early stages of metal corrosion in tin bronze. This work provided a facile strategy for the monitoring of metal corrosion.
Food stability refers to a state of consistent and reliable access to key dietary resources and is a crucial factor in the resilience and growth of communities throughout history. The study of human diets has been a focus of archaeological research over recent decades. Isotopic analyses provide unique insight into the breadth and evolution of food consumption, often reflecting broader environmental and social shifts while also indicating human resilience and adaptability to various stressors. Rarely, however, are we able to observe subsistence economies over extended periods within the same archaeologically defined cultural group. This research is the first isotopic project on Bronze Age diet of the Moriš culture (roughly 2700-1500 BCE), and one of the few isotopic studies in the Carpathian Basin. This research presents stable carbon and nitrogen isotopic data from human and animal bone collagen recovered at four Moriš sites. This includes two cemeteries (Mokrin and Ostojićevo) and two settlements (Kiszombor Új Élet and Klárafalva Hajdova), all located within the southern Carpathian Basin. Isotopic analysis of human collagen reveals minimal variation among individuals buried in the cemeteries over the span of 550 years (2100-1550 BCE). Overall, there was food stability during the Early and Late Moriš, with only a slight change in diet towards the end of the Late Moriš period.
In this work, protonated tungsten bronze powder (HxWO3) was synthesized by a microwave heating technique from tungsten(VI) chloride in benzyl alcohol. This material facilitates a proton-coupled electron transfer (PCET) reaction with 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) in toluene, an aprotic solvent, to form TEMPOH, evidenced by UV-vis analysis of the organic product and X-ray photoelectron spectroscopy (XPS) analysis showing the oxidation of W5+ to W6+ in the remaining powder. Then, under illumination in an acidic aqueous solution, the oxidized WO3 powder reacts photochromically to regenerate HxWO3. The regenerated HxWO3 reagent remains active for further PCET reactions.
Bacterial biofilms are a persistent challenge in industrial settings such as water treatment and food processing, contributing to antimicrobial resistance, operational inefficiencies, and environmental burden. Here, we report on the synthesis and multiscale evaluation of hydrogen molybdenum bronze nanosheets (HMB-NSHs) and their silver-decorated nanotube derivatives (Ag-decorated HMB-NTs), produced via an arc discharge method. High-resolution structural analyses revealed crystalline, ultrathin HMB sheets and tubular architectures adorned with uniformly distributed Ag nanoparticles (∼3-5 nm). While HMB-NSHs were biologically inert, Ag-decorated HMB-NTs demonstrated potent antibacterial effects against Bacillus subtilis, inhibiting planktonic growth (75.7%), biofilm formation (77.7%), and biofilm eradication (64.3%) at 25 μg/mL. Complementary SEM and fluorescence microscopy visualizations revealed pronounced morphological membrane damage such as wrinkling, roughening, and biofilm reduction signatures absent in control and HMB-treated samples, facilitating metal ion deposition and localized oxidative stress. At the molecular level, multiscale computational modeling, including molecular docking, DFT, QTAIM, RDG, and IGM analyses, provided atomic-resolution insights into dual-site antibacterial action. The Ag and HMB moieties interact favorably with both the cell-wall penicillin-binding protein (PDB ID: 4WO7) and intracellular division regulator FtsZ (PDB ID: 2VAM), forming energetically stable complexes. QTAIM metrics confirmed extensive van der Waals and hydrogen bonding networks with 4WO7, whereas RDG and IGM surfaces visualized dense noncovalent contact regions. Ag-FtsZ interactions, though weaker, suggest possible disruption of cell cycle machinery upon internalization. These findings establish Ag-decorated HMB-NTs as a dual-function nanomaterial: HMB scaffolds promote surface adhesion and stability, whereas Ag enables membrane destabilization and intracellular disruption. Together, these processes highlight membrane damage and protein interference as the primary antibacterial mechanisms, underscoring their potential as a next-generation antibacterial platform, particularly against biofilm-forming and industrially relevant bacteria such as Bacillus subtilis.
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Accurate species delimitation is essential for understanding biodiversity patterns and guiding conservation, yet cryptic species with minimal morphological variation often obscure the assessment of true species diversity, making the identification of reliable diagnostic characters critical. Island radiations exemplify this challenge by concentrating endemic diversity in restricted areas, which accentuates both the urgency of conservation and the need for accurate taxonomy, while often presenting species divergences masked by subtle morphological differences. Here, we investigated patterns of morphological differentiation in Ailuronyx geckos, a genus endemic to the Seychelles archipelago, comprising deeply divergent lineages and unresolved, possibly cryptic species boundaries. We applied 3D and 2D morphometric analyses across the range (16 islands) of the three recognised species: the bronze-eyed gecko A. seychellensis, dwarf bronze gecko A. tachyscopaeus, and giant bronze gecko A. trachygaster. 3D geometric morphometric analyses of cranial and mandibular landmark data from 42 geckos revealed strong species-level differences. Ailuronyx trachygaster exhibits extreme skull sculpturing with rugose textures on up to ten cranial and three mandibular bones, while the other two species have smooth skull surfaces. Skull elongation and narrowing increased with decreasing body size from the larger A. trachygaster, via the medium-sized A. seychellensis, to the smaller A. tachyscopaeus. Analysis of body size-corrected 2D measurements of ten external morphological traits from 567 geckos revealed similar differences in head dimensions among the species, but also showed changes in mass and toe length. While we observed substantial morphological variation between islands, we did not find support for the previously identified northern and southern island group divergence within either A. seychellensis or A. tachyscopaeus. Nevertheless, we found strong support for the proposed divergence between northern and southern Mahé populations of A. tachyscopaeus, with variation in mass and head size between the two populations. We provide morphometric parameters to guide species identification within this gecko genus and highlight distinct population units that warrant further genomic investigation and prioritisation for conservation. Our findings illustrate the complexity of morphological diversification in archipelagos, where island-specific processes may outweigh regional biogeographic patterns. This underscores the need for integrative approaches to species delimitation and conservation in insular systems. The online version contains supplementary material available at 10.1186/s12862-026-02517-9.
This study examines the residential mobility patterns and funerary practices of an Urnfield cemetery at Přáslavice, Czech Republic, using radiocarbon dating, carbon, oxygen, and strontium isotope analyses, and FTIR analysis. A regional bioavailable strontium baseline map was created using strontium isotope ratios (87Sr/86Sr) of modern plant samples (n=208) from 70 localities across Moravia and Czech Silesia. Radiocarbon dates (n=17) suggest that the cemetery was primarily in use during the Late Bronze Age (1300-1100 BCE), with some burials dated to the Final Bronze Age (1100-800 BCE). Most of the Late Bronze Age burials have homogenous 87Sr/86Sr values (0.7114-0.7128) well within the established local Sr baseline, thus supporting the hypothesis that Urnfield at Přáslavice was a local development. FTIR and carbon and oxygen isotope analyses also suggest the group practiced cremation similarly to other Urnfield populations. Overall, this study not only enhances our knowledge of the social dynamics and funerary practices at Přáslavice, but also establishes a crucial bioavailable Sr baseline for future palaeomobility studies in the region. The online version contains supplementary material available at 10.1007/s12520-026-02436-2.
The eastern Tianshan range in Xinjiang, serving as a crucial link between the East and the West, acts as an important channel for the eastward spread of East Asian millet and painted pottery, as well as the westward diffusion of West Asian wheat and barley, bronze wares, and livestock. However, due to the scarcity of ancient genomic data, the history of population interaction and admixture in this region remains unclear. We sequenced 23 ancient individuals from 12 archaeological sites from the Bronze Age to historical periods in Xinjiang. We identified intraregional population interactions, demonstrating that an indigenous local ancestry, represented by Tarim_EMBA1, spread to the Tianshan and persisted into the historical period. The incoming East Asian millet farmers, along with Western Steppe herders characterized by Afanasievo, contributed to the formation of the eastern Tianshan populations during the Iron Age, which is consistent with archaeological findings of painted pottery and pastoral subsistence in this area. The genetic affinity to East Asian millet farmers in the eastern Tianshan increased over time, likely reflecting geographic proximity and geopolitical changes. In contrast, in line with archaeological observations, the Iron Age individuals in the western Tianshan derived their Steppe-related ancestry from populations associated with the Andronovo culture. Our results illustrated the interplay between genetics and culture in the eastern Tianshan.