More Like this

1. In‐situ Sourcing of Hematite Paints on the Surface of Hohokam Red‐on‐Buff Ceramics Using Laser Ablation – Inductively Coupled Plasma – Mass Spectrometry (LA–ICP–MS) and Instrumental Neutron Activation Analysis

   https://doi.org/10.1111/arcm.12427  

   Eiselt, B. S. ; Dudgeon, J. ; Darling, J. A. ; Paucar, E. N. ; Glascock, M. D. ; Woodson, M. K. ( October 2018 , Archaeometry)

   Worldwide applications of ochre analysis continue to develop at a rapid pace, highlighting a number of analytical and interpretative issues. As regional source databases continue to grow, researchers have turned to the thornier issues of source allocation. In this study, we utilize LA–ICP–MS and NAA to examine archaeological pigments, ceramic paints and experimental tiles from geological sources and Hohokam ceramics in central Arizona. Archaeological pigments and paint on sherds are successfully source matched based on trace element content, with implications for understanding paint production, sociocultural relations governing trade in pigment and the use of different resource landscapes over time.

    

   more » « less
2. New light on the use of Theobroma cacao by Late Classic Maya

   https://doi.org/10.1073/pnas.2121821119  

   Ford, Anabel ; Williams, Ann ; de Vries, Mattanjah S. ( October 2022 , Proceedings of the National Academy of Sciences)

   Cacao seeds, Theobroma cacao , provide the basis for a ceremonially important Mesoamerican food. Past efforts to identify cacao in ceramics focused on highly decorative vessel forms associated with elite ceremonial contexts, creating assumptions as to how cacao was distributed and who could access it. This study examines 54 archaeological ceramic sherds from El Pilar (Belize/Guatemala) of Late Classic (600 to 900 CE) residential and civic contexts representing a cross-section of ancient Maya inhabitants. Identification of cacao in ancient sherds has depended on the general presence of theobromine; we used the discrete presence of theophylline, a unique key biomarker for cacao in the region. Analysis was done by grinding off all outside surfaces to reduce contamination, pulverizing the inner clay matrix, extracting absorbed molecules, and concentrating the extractions. In order to obtain especially high selectivity and low limits of detection, our study utilized the technique of resonance-enhanced multiphoton ionization coupled with laser-desorption jet-cooling mass spectrometry. This technique isolates molecules in the cold gas phase where they can be selectively ionized through a resonant two-photon process. Of the sherds analyzed, 30 samples (56%) were found to contain significant amounts of theophylline and thus test positive for cacao. Importantly, cacao is present in all contexts, common to all Maya residents near and far from centers. 

   more » « less
3. Expedition 391 summary

   Sager, W. ; Hoernle, K. ; Höfig, T.W. ; Avery, A.J. ; Bhutani, R. ; Buchs, D.M. ; Carvallo, C.A. ; Class, C. ; Dai, Y. ; Dalla Valle, G. ; et al ( October 2023 , Proceedings of the International Ocean Discovery Program Expedition reports)

   Hotspot tracks (chains of seamounts, ridges, and other volcanic structures) provide important records of plate motions, as well as mantle geodynamics, magma flux, and mantle source compositions. The Tristan-Gough-Walvis Ridge (TGW) hotspot track, extending from the active volcanic islands of Tristan da Cunha and Gough through a province of guyots and then along Walvis Ridge to the Etendeka flood basalt province, forms one of the most prominent and complex global hotspot tracks. The TGW hotspot track displays a tight linear age progression in which ages increase from the islands to the flood basalts (covering ~135 My). Unlike Pacific tracks, which are often simple, nearly linear chains of seamounts, the TGW track is alternately a steep-sided narrow ridge, an oceanic plateau, subparallel linear ridges and chains of seamounts (most are flat-topped guyots). The track displays isotopic zonation over the last ~70 My. The zonation appears near the middle of the track just before it splits into two to three chains of ridge- and guyot-type seamounts. Walvis Ridge, forming the older part of the track, is also overprinted with age-progressive late-stage volcanism, which was emplaced ~30–40 My after the initial eruptions and has a distinct isotopic composition. The plan for Expedition 391 was to drill at six sites, three along Walvis Ridge and three in the seamounts of the Guyot Province, to collect igneous rocks to better understand the formation of volcanic edifices, the temporal and geochemical evolution of the hotspot, and the variation in paleolatitudes at which the volcanic edifices formed. After a delay of 18 days to address a shipboard Coronavirus (COVID-19) outbreak, Expedition 391 proceeded to drill at four of the proposed sites: three sites on Walvis Ridge around Valdivia Bank, an ocean plateau within the ridge, and one site on the lower flank of a guyot in the Center track of the Guyot Province, a ridge located between the Tristan subtrack (which extends from the end of Walvis Ridge to the islands of Tristan da Cunha) and the Gough subtrack (which extends from Walvis Ridge to Gough Island). The first hole was drilled at Site U1575, located on a low portion of the northeastern Walvis Ridge just north of Valdivia Bank. At this location, 209.9 m of sediments and 122.4 m of igneous basement were cored. The sediments ranged in age from Late Pleistocene (~0.43–1.24 Ma) to Late Cretaceous (Campanian; 72–78 Ma). The igneous basement comprised 10 submarine lava units consisting of pillow, lobate, sheet, and massive lava flows, the thickest of which was ~21 m. Most lavas are tholeiitic, but some alkalic basalts were recovered. A portion of the igneous succession consists of low-Ti basalts, which are unusual because they appear in the Etendeka flood basalts but have not been previously found on Walvis Ridge. Two holes were drilled at Site U1576 on the west flank of Valdivia Bank. The first of these holes was terminated because a bit jammed shortly after entering the igneous basement. Hole U1576A recovered a remarkable ~380 m thick sedimentary section consisting mostly of chalk covering a nearly complete sequence from Late Pleistocene (~0.43–1.24 Ma) to Late Cretaceous (Campanian; ~79–81.38 Ma). These sediments display short and long cyclic color changes that imply astronomically forced and longer term paleoenvironmental changes. The igneous basement recovered in Hole U1576B yielded 11 submarine lava units (total thickness = ~65 m). The flows range from pillows to massive flows with compositions varying from tholeiitic basalt to basaltic andesite, only the second occurrence of the latter composition recovered from the TGW track thus far. These units are separated by seven sedimentary chalk units that range 0.1–11.6 m in thickness, implying a long-term interplay of sedimentation and lava eruptions. These intercalated sediments revealed Upper Cretaceous (Campanian) ages of ~77–79 Ma for the upper two interbeds and ~79–81.38 Ma for the lower beds. Coring at Site U1577, on the extreme eastern flank of Valdivia Bank, penetrated a 154.8 m thick sedimentary section ranging from the Paleocene (Thanetian; ~58.8 Ma) to Upper Cretaceous (Campanian; ~81.43–83.20 Ma). Igneous basement coring progressed only 39.1 m below the sediment/basalt contact, recovering three massive submarine tholeiitic basalt lava flows that are 4.1, 15.5, and >19.1 m thick, respectively. Paleomagnetic data from Sites U1577 and U1576 indicate that the former volcanic basement formed just before the end of the Cretaceous Normal Superchron and the latter during Chron 33r, shortly afterward. Biostratigraphic and paleomagnetic data suggest that Valdivia Bank becomes younger from east to west. Site U1578, located on a Center track guyot, provided a long and varied igneous section. After coring through 184.3 m of pelagic carbonate sediments mainly consisting of Eocene and Paleocene chalk (~55.64–63.5 Ma), Hole U1578A cored 302.1 m of igneous basement. Basement lavas are largely pillows but are interspersed with sheet and massive flows. Lava compositions are mostly alkalic basalts with some hawaiite. Several intervals contain abundant olivine (some fresh), and some of the pillow stacks consist of basalt with remarkably high Ti content. The igneous sequence is interrupted by 10 sedimentary interbeds consisting of chalk and volcaniclastics and ranging 0.46–10.19 m in thickness. Investigations of toothpick samples from the intercalated sediments were examined, each revealing the same age range of ~63.5–64.81 Ma (lower Paleocene; Danian). Paleomagnetic data display a change in basement magnetic polarity ~100 m above the base of the hole. Combining magnetic stratigraphy with biostratigraphic data, the igneous section is inferred to span >1 My. Nearly 7 months after Expedition 391, JOIDES Resolution transited from Cape Town to the north Atlantic. During this transit (Expedition 397T), 7.9 days of ship time were used to drill two holes (U1584A and U1585A) at sites on the Gough and Tristan tracks that had been omitted because of COVID-19–related time loss on the earlier cruise. For both, coring was begun only a short distance above the igneous basement to save time. The 75.2 m thick section drilled in Hole U1584A contains two sedimentary units: clay-rich carbonate sediments overlie a pumice-dominated volcaniclastic deposit containing basalt fragments. Because the goal was to core basalt and the base of the volcaniclastic deposit was not imaged in the seismic profile, the hole was terminated early to save operation time for the next site. In Hole U1585A, coring penetrated a 273.5 m thick sediment section overlying an 81.2 m thick pile of massive basalt flows. The sediment section is divided into four units: The uppermost unit consists of nannofossil chalk; The two intermediate units contain alternating chalk and volcaniclastic sediments containing several breccia units; and The lowermost unit consists of volcanic breccia containing juvenile blocks, bombs, and accretionary lapilli. This thick sedimentary section documents a transition from shallow-water volcanism to open-ocean sedimentation as the seamount subsided. The thick underlying basalt section is made up of four sparsely to highly phyric massive flows, the thickest of which is >43 m thick. Samples of these units are mostly basalt with a few trachybasalts and one trachyandesite. Although the igneous penetration was less than planned, coring during Expeditions 391 and 397T obtained samples that clearly will lead to an improved understanding of the evolution of the TGW hotspot and its track. Reasonable recovery of fresh basalt in some holes provides ample samples for geochemical, geochronologic, and paleomagnetic studies. Good recovery of Late Cretaceous and early Cenozoic chalk successions provides samples for paleoenvironmental study. 

   more » « less
4. Enhanced Piezoelectric, Ferroelectric, and Electrostrictive Properties of Lead‐Free (1‐ x )BCZT‐( x )BCST Electroceramics with Energy Harvesting Capability

   https://doi.org/10.1002/smll.202300549  

   Baraskar, Bharat G. ; Kolekar, Yesappa D. ; Thombare, Balu. R. ; James, Ajit. R. ; Kambale, Rahul C. ; Ramana, C. V. ( May 2023 , Small)

   Next‐generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)‐free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi‐phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead‐free piezoelectric materials (1‐x)Ba_0.95Ca_0.05Ti_0.95Zr_0.05O₃‐(x)Ba_0.95Ca_0.05Ti_0.95Sn_0.05O₃, are reported, which are represented as (1‐x)BCZT‐(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1‐x)BCZT‐(x)BCST materials are synthesized by high‐temperature solid‐state ceramic reaction method by varyingxin the full range (x= 0.00–1.00). In‐depth exploration research is performed on the structural, dielectric, ferroelectric, and electro‐mechanical properties of (1‐x)BCZT‐(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X‐ray diffraction (XRD) analyses, which also reveals that the Ca²⁺, Zr⁴⁺, and Sn⁴⁺are well dispersed within the BaTiO₃lattice. For all (1‐x)BCZT‐(x)BCST ceramics, thorough investigation of phase formation and phase‐stability using XRD, Rietveld refinement, Raman spectroscopy, high‐resolution transmission electron microscopy (HRTEM), and temperature‐dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2+P4mm) phases at room temperature. The steady transition ofAmm2crystal symmetry toP4mmcrystal symmetry with increasingxcontent is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral‐orthorhombic (T_R‐O), orthorhombic‐ tetragonal (T_O‐T), and tetragonal‐cubic (T_C), gradually shift toward lower temperature with increasingxcontent. For (1‐x)BCZT‐(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constantε_r≈ 1900–3300 (near room temperature),ε_r≈ 8800–12 900 (near Curie temperature), dielectric loss, tanδ≈ 0.01–0.02, remanent polarizationP_r≈ 9.4–14 µC cm⁻², coercive electric fieldE_c≈ 2.5–3.6 kV cm⁻¹. Further, high electric field‐induced strainS≈ 0.12–0.175%, piezoelectric charge coefficientd₃₃≈ 296–360 pC N⁻¹, converse piezoelectric coefficient ≈ 240–340 pm V⁻¹, planar electromechanical coupling coefficientk_p≈ 0.34–0.45, and electrostrictive coefficient (Q₃₃)_avg≈ 0.026–0.038 m⁴C⁻²are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT‐(0.4)BCST composition (x= 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead‐free piezoelectric (1‐x)BCZT‐(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1‐x)BCZT‐(x)BCST ceramics as a potentially strong contender within the family of Pb‐free piezoelectric materials for future electronics and energy harvesting device technologies.

    

   more » « less
5. Near-zero 33S and 36S anomalies in Pitcairn basalts suggest Proterozoic sediments in the EM-1 mantle plume

   https://doi.org/10.1016/j.epsl.2022.117422  

   Labidi, Jabrane ; Dottin, James W. ; Clog, Matthieu ; Hemond, Christophe ; Cartigny, Pierre ( April 2022 , Earth and planetary science letters)

   Volcanic rocks erupted among Pitcairn seamounts sample a mantle plume that exhibits an extreme Enriched Mantle-1 signature. The origin of this peculiar mantle endmember remains contentious, and could involve the recycling of marine sediments of Archean or Proterozoic ages, delaminated units from the lower continental crust, or metasomatized peridotites from a lithospheric mantle. Here, we report the sulfur multi-isotopic signature (32S, 33S, 34S, 36S) of 15 fresh submarine basaltic glasses from three Pitcairn seamounts. We observe evidence for magmatic degassing of sulfur from melts erupted ∼2,000 meters below seawater level (mbsl). Sulfur concentrations are correlated with eruption depth, and range between 1300 ppm S (collected ∼ 2,500 mbsl) and 600 ppm S (∼2,000 mbsl). The δ34S values can be accounted for under equilibrium isotope fractionation during degassing, with αgas-melt between 1.0020 and 1.0001 and starting δ34S values between −0.9‰ and +0.6‰. The δ34S estimates are similar or higher than MORB signatures, suggesting the contribution of recycled sulfur with a ∼ 1‰ 34S enrichment compared to the Pacific upper mantle. The Δ33S and Δ36S signatures average at +0.024±0.007‰ and +0.02±0.07‰ vs. CDT, respectively (all 1σ). Only Δ33S is statistically different from MORB, by +0.02‰. The Δ33S enrichment is invariant across degassing and sulfide segregation. We suggest it reflects a mantle source enrichment rather than a high-temperature fractionation of S in the basalts. Despite the small magnitude of the 33S-36S variations, our data require a substantial amount of recycled sulfur overwhelm the Pitcairn mantle source. We show that models involving metasomatized peridotites, lower crust units, or Archean sediments, may be viable, but are restricted to narrow sets of circumstances. Instead, scenarios involving the contribution of Proterozoic marine sediments appear to be the most parsimonious explanation for the EM-1 signature at Pitcairn. 

   more » « less