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Emerging epidemiological studies suggest that long-term ozone (O 3 ) exposure may increase the risk of mortality, while pre-existing evidence is mixed and has been generated predominantly in North America and Europe. In this study, we investigated the impact of long-term O 3 exposure on all-cause mortality in a national cohort in China. A dynamic cohort of 20882 participants aged ≥40 years was recruited between 2011 and 2018 from four waves of the China Health and Retirement Longitudinal Study. A Cox proportional hazard regression model with time-varying exposures on an annual scale was used to estimate the mortality risk associated with warm-season (April-September) O 3 exposure. The annual average level of participant exposure to warm-season O 3 concentrations was 100 μg m -3 (range: 61-142 μg m -3 ). An increase of 10 μg m -3 in O 3 was associated with a hazard ratio (HR) of 1.18 (95% confidence interval [CI]: 1.13-1.23) for all-cause mortality. Compared with the first exposure quartile of O 3 , HRs of mortality associated with the second, third, and highest exposure quartiles were 1.09 (95% CI: 0.95-1.25), 1.02 (95% CI: 0.88-1.19), and 1.56 (95% CI: 1.34-1.82), respectively. A J-shaped concentration-response association was observed, revealing a non-significant increase in risk below a concentration of approximately 110 μg m -3 . Low-temperature-exposure residents had a higher risk of mortality associated with long-term O 3 exposure. This study expands current epidemiological evidence from China and reveals that high-concentration O 3 exposure curtails the long-term survival of middle-aged and older adults., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Domain walls and specifically ferroelastic twin boundaries are depositaries and fast diffusion pathways for chemical dopants and intrinsic lattice defects. Ferroelastic domain patterns act as templates for chemical structures where the walls are the device and not the bulk. Several examples of such engineered domain boundaries are given. Moving twin boundaries are shown to carry with them the dopants, although the activation of this mechanism depends sensitively on the applied external force. If the force is too weak, the walls remain pinned while too strong forces break the walls free of the dopants and move them independently. Several experimental methods and approaches are discussed.

A potential record of Earth's magnetic field going back 4.2 billion years (Ga) ago is carried by magnetite inclusions in zircon grains from the Jack Hills. This magnetite may be secondary in nature, however, meaning that the magnetic record is much younger than the zircon crystallization age. Here, we use atom probe tomography to show that Pb-bearing nanoclusters in magnetite-bearing Jack Hills zircons formed during two discrete events at 3.4 and <2 Ga. The older population of clusters contains no detectable Fe, whereas roughly half of the younger population of clusters is Fe bearing. This result shows that the Fe required to form secondary magnetite entered the zircon sometime after 3.4 Ga and that remobilization of Pb and Fe during an annealing event occurred more than 1 Ga after deposition of the Jack Hills sediment at 3 Ga. The ability to date Fe mobility linked to secondary magnetite formation provides new possibilities to improve our knowledge of the Archean geodynamo.

The cations of an ordered omphacite from the Tauern window were gradually disordered in piston cylinder experiments at temperatures between 850 and 1150 °C. The samples were examined by X-ray powder diffraction and then investigated using low-temperature calorimetry and IR spectroscopy. The low-temperature heat capacity data were used to obtain the vibrational entropies, and the line broadening of the IR spectra served as a tool to investigate the disordering enthalpy. These data were then used to calculate the configurational entropy as a function of temperature. The vibrational entropy does not change during the cation ordering phase transition from space group C2/c to P2/n at 865 °C but increases with a further temperature increase due to the reduction of short-range order., Supplementary Information: The online version contains supplementary material available at 10.1007/s00269-023-01260-7., Competing Interests: Conflict of interestThe authors declare no competing interests., (© The Author(s) 2023.)

The eruptions of Eyjafjallajökull volcano in 2010 (including its initial effusive phase at Fimmvörðuháls and its later explosive phase from the central volcano) and Bárðarbunga volcano in 2014-2015 (at Holuhraun) were widely reported. Here, we report on complementary, interdisciplinary observations made of the eruptive gases and lavas that shed light on the processes and atmospheric impacts of the eruptions, and afford an intercomparison of contrasting eruptive styles and hazards. We find that (i) consistent with other authors, there are substantial differences in the gas composition between the eruptions; namely that the deeper stored Eyjafjallajökull magmas led to greater enrichment in Cl relative to S; (ii) lava field SO 2 degassing was measured to be 5-20% of the total emissions during Holuhraun, and the lava emissions were enriched in Cl at both fissure eruptions-particularly Fimmvörðuháls; and (iii) BrO is produced in Icelandic plumes in spite of the low UV levels., Supplementary Information: The online version contains supplementary material available at 10.1007/s11069-023-06114-7., Competing Interests: Conflict of interestThe authors declare that they have no competing interests., (© The Author(s) 2023.)

The Paleocene-Eocene Thermal Maximum (PETM) was an abrupt global warming event associated with a large injection of carbon into the ocean-atmosphere system, as evidenced by a diagnostic carbon isotope excursion (CIE). Evidence also suggests substantial hydrologic perturbations, but details have been hampered by a lack of appropriate proxies. To address this shortcoming, here we isolate and measure the isotopic composition of hydroxyl groups (OH - ) in clay minerals from a highly expanded PETM section in the North Sea Basin, together with their bulk oxygen isotope composition. At this location, we show that hydroxyl O- and H-isotopes are less influenced than bulk values by clay compositional changes due to mixing and/or inherited signals and thus better track hydrologic variability. We find that clay OH - hydrogen-isotope values (δ 2 H OH ) decrease slowly prior to the PETM and then abruptly by ∼8‰ at the CIE onset. Coincident with an increase in relative kaolinite content, this indicates increased rainfall and weathering and implies an enhanced hydrologic cycle response to global warming, particularly during the early stages of the PETM. Subsequently, δ 2 H OH returns to pre-PETM values well before the end of the CIE, suggesting hydrologic changes in the North Sea were short-lived relative to carbon-cycle perturbations., (© 2022. The Author(s).)

Adult molluscs produce shells with diverse morphologies and ornamentations, different colour patterns and microstructures. The larval shell, however, is a phenotypically more conserved structure. How do developmental and evolutionary processes generate varying diversity at different life-history stages within a species? Using live imaging, histology, scanning electron microscopy and transcriptomic profiling, we have described shell development in a heteroconchian bivalve, the Antarctic clam, Laternula elliptica, and compared it to adult shell secretion processes in the same species . Adult downstream shell genes, such as those encoding extracellular matrix proteins and biomineralization enzymes, were largely not expressed during shell development. Instead, a development-specific downstream gene repertoire was expressed. Upstream regulatory genes such as transcription factors and signalling molecules were largely conserved between developmental and adult shell secretion. Comparing heteroconchian data with recently reported pteriomorphian larval shell development data suggests that, despite being phenotypically more conserved, the downstream effectors constituting the larval shell 'tool-kit' may be as diverse as that of adults. Overall, our new data suggest that a larval shell formed using development-specific downstream effector genes is a conserved and ancestral feature of the bivalve lineage, and possibly more broadly across the molluscs., (© 2022 The Authors.)

Ichthyornis has long been recognized as a pivotally important fossil taxon for understanding the latest stages of the dinosaur-bird transition, but little significant new postcranial material has been brought to light since initial descriptions of partial skeletons in the 19 th Century. Here, we present new information on the postcranial morphology of Ichthyornis from 40 previously undescribed specimens, providing the most complete morphological assessment of the postcranial skeleton of Ichthyornis to date. The new material includes four partially complete skeletons and numerous well-preserved isolated elements, enabling new anatomical observations such as muscle attachments previously undescribed for Mesozoic euornitheans. Among the elements that were previously unknown or poorly represented for Ichthyornis , the new specimens include an almost-complete axial series, a hypocleideum-bearing furcula, radial carpal bones, fibulae, a complete tarsometatarsus bearing a rudimentary hypotarsus, and one of the first-known nearly complete three-dimensional sterna from a Mesozoic avialan. Several pedal phalanges are preserved, revealing a remarkably enlarged pes presumably related to foot-propelled swimming. Although diagnosable as Ichthyornis , the new specimens exhibit a substantial degree of morphological variation, some of which may relate to ontogenetic changes. Phylogenetic analyses incorporating our new data and employing alternative morphological datasets recover Ichthyornis stemward of Hesperornithes and Iaceornis , in line with some recent hypotheses regarding the topology of the crownward-most portion of the avian stem group, and we establish phylogenetically-defined clade names for relevant avialan subclades to help facilitate consistent discourse in future work. The new information provided by these specimens improves our understanding of morphological evolution among the crownward-most non-neornithine avialans immediately preceding the origin of crown group birds., Competing Interests: The authors declare that they have no competing interests., (© 2022 Benito et al.)

Particulate matter (PM) concentration levels in the London Underground (LU) are higher than London background levels and beyond World Health Organization (WHO) defined limits. Wheel, track, and brake abrasion are the primary sources of particulate matter, producing predominantly Fe-rich particles that make the LU microenvironment particularly well suited to study using environmental magnetism. Here we combine magnetic properties, high-resolution electron microscopy, and electron tomography to characterize the structure, chemistry, and morphometric properties of LU particles in three dimensions with nanoscale resolution. Our findings show that LU PM is dominated by 5-500 nm particles of maghemite, occurring as 0.1-2 μm aggregated clusters, skewing the size-fractioned concentration of PM artificially to larger sizes when measured with traditional monitors. Magnetic properties are largely independent of the PM filter size (PM 10 , PM 4 , and PM 2.5 ), and demonstrate the presence of superparamagnetic (< 30 nm), single-domain (30-70 nm), and vortex/pseudo-single domain (70-700 nm) signals only (i.e., no multi-domain particles > 1 µm). The oxidized nature of the particles suggests that PM exposure in the LU is dominated by resuspension of aged dust particles relative to freshly abraded, metallic particles from the wheel/track/brake system, suggesting that periodic removal of accumulated dust from underground tunnels might provide a cost-effective strategy for reducing exposure. The abundance of ultrafine particles identified here could have particularly adverse health impacts as their smaller size makes it possible to pass from lungs to the blood stream. Magnetic methods are shown to provide an accurate assessment of ultrafine PM characteristics, providing a robust route to monitoring, and potentially mitigating this hazard., (© 2022. The Author(s).)

The bony palate diagnoses the two deepest clades of extant birds: Neognathae and Palaeognathae 1-5 . Neognaths exhibit unfused palate bones and generally kinetic skulls, whereas palaeognaths possess comparatively rigid skulls with the pterygoid and palatine fused into a single element, a condition long considered ancestral for crown birds (Neornithes) 3,5-8 . However, fossil evidence of palatal remains from taxa close to the origin of Neornithes is scarce, hindering strong inferences regarding the ancestral condition of the neornithine palate. Here we report a new taxon of toothed Late Cretaceous ornithurine bearing a pterygoid that is remarkably similar to those of the extant neognath clade Galloanserae (waterfowl + landfowl). Janavis finalidens, gen. et sp. nov., is generally similar to the well-known Mesozoic ornithurine Ichthyornis in its overall morphology, although Janavis is much larger and exhibits a substantially greater degree of postcranial pneumaticity. We recovered Janavis as the first-known well-represented member of Ichthyornithes other than Ichthyornis, clearly substantiating the persistence of the clade into the latest Cretaceous 9 . Janavis confirms the presence of an anatomically neognathous palate in at least some Mesozoic non-crown ornithurines 10-12 , suggesting that pterygoids similar to those of extant Galloanserae may be plesiomorphic for crown birds. Our results, combined with recent evidence on the ichthyornithine palatine 12 , overturn longstanding assumptions about the ancestral crown bird palate, and should prompt reevaluation of the purported galloanseran affinities of several bizarre early Cenozoic groups such as the 'pseudotoothed birds' (Pelagornithidae) 13-15 ., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Heavy metals in coastal waters are a great environmental concern in the North Sea since the middle of the 20th century. Regulatory efforts have led to a significant reduction in atmospheric and water-transported heavy metals. Still, high concentrations of these in sediments remain a risk for ecosystems, requiring close monitoring. Here, we investigated the applicability of Nucella lapillus museum collections as a tool for targeted tracking of chronic anthropogenic heavy metal pollution. We analysed the concentration ratios of the common heavy metals Cu, Cd, Pb, and Zn in relation to Ca in N. lapillus shells collected from the Dutch and Belgian intertidal zone over the last 130 years. We found that shell Cu/Ca and Zn/Ca concentration ratios remained remarkably constant, whereas Pb/Ca concentration trends were closely aligned with emissions of leaded petrol in Europe. Our results suggest that N. lapillus provides a suitable Pb pollution archive of the intertidal zone., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Collocated crystal sizes and mineral identities are critical for interpreting textural relationships in rocks and testing geological hypotheses, but it has been previously impossible to unambiguously constrain these properties using in situ instruments on Mars rovers. Here, we demonstrate that diffracted and fluoresced x-rays detected by the PIXL instrument (an x-ray fluorescence microscope on the Perseverance rover) provide information about the presence or absence of coherent crystalline domains in various minerals. X-ray analysis and multispectral imaging of rocks from the Séítah formation on the floor of Jezero crater shows that they were emplaced as coarsely crystalline igneous phases. Olivine grains were then partially dissolved and filled by finely crystalline or amorphous secondary silicate, carbonate, sulfate, and chloride/oxychlorine minerals. These results support the hypothesis that Séítah formation rocks represent olivine cumulates altered by fluids far from chemical equilibrium at low water-rock ratios.

Plasmonic nanoparticles (NPs) have garnered excitement over the past several decades stemming from their unique optoelectronic properties, leading to their use in various sensing applications and theranostics. Symmetry dictates the properties of many nanomaterials, and nanostructures with low, but still defined symmetries, often display markedly different properties compared to their higher symmetry counterparts. While numerous methods are available to manipulate symmetry, surface protecting groups such as polymers are finding use due to their ability to achieve regioselective modification of NP seeds, which can be removed after overgrowth as shown here. Specifically, poly(styrene- b -polyacrylic acid) (PSPAA) is used to asymmetrically passivate cubic Au seeds through competition with hexadecyltrimethylammonium bromide (CTAB) ligands. The asymmetric passivation via collapsed PSPAA causes only select vertices and faces of the Au cubes to be available for deposition of new material ( i.e. , Au, Au-Ag alloy, and Au-Pd alloy) during seeded overgrowth. At low metal precursor concentrations, deposition follows observations from unpassivated seeds but with new material growing from only the exposed seed portions. At high metal precursor concentrations, nanobowl-like structures form from interaction between the depositing phase and the passivating PSPAA. Through experiment and simulation, the optoelectronic properties of these nanobowls were probed, finding that the interiors and exteriors of the nanobowls can be functionalized selectively as revealed by surface enhanced Raman spectroscopy (SERS).

Metal-organic framework crystal-glass composites (MOF CGCs) are a class of materials comprising a crystalline framework embedded within a MOF glass matrix. Herein, we investigate the thermal expansion behavior of three MOF CGCs, incorporating two flexible (MIL-53(Al) and MIL-118) and one rigid (UL-MOF-1) MOF within a ZIF-62 glass matrix. Specifically, variable-temperature powder X-ray diffraction data and thermomechanical analysis show the suppression of thermal expansivity in each of these three crystalline MOFs when suspended within a ZIF-62 glass matrix. In particular, for the two flexible frameworks, the average volumetric thermal expansion (β) was found to be near-zero in the crystal-glass composite. These results provide a route to engineering thermal expansivity in stimuli-responsive MOF glass composites.

Exposure measurement error is an important source of bias in epidemiological studies. We assessed the validity of employing ambient (outdoor) measurements as proxies of personal exposures at individual levels focusing on fine particles (PM 2.5 ) and black carbon (BC)/elemental carbon (EC) on a global scale. We conducted a systematic review and meta-analysis and searched databases (ISI Web of Science, Scopus, PubMed, Ovid MEDLINE®, Ovid Embase, and Ovid BIOSIS) to retrieve observational studies in English language published from 1 January 2006 until 5 May 2021. Correlation coefficients (r) between paired ambient (outdoor) concentration and personal exposure for PM 2.5 or BC/EC were standardized as effect size. We used random-effects meta-analyses to pool the correlation coefficients and investigated the causes of heterogeneity and publication bias. Furthermore, we employed subgroup and meta-regression analyses to evaluate the modification of pooled estimates by potential mediators. This systematic review identified thirty-two observational studies involving 1744 subjects from ten countries, with 28 studies for PM 2.5 and 11 studies for BC/EC. Personal PM 2.5 exposure is more strongly correlated with ambient (outdoor) concentrations (0.63, 95% confidence interval [CI]: 0.57-0.68) than personal BC/EC exposure (0.49, 95% CI: 0.38-0.59), with significant differences in ṝ (0.14, 95% CI: 0.03-0.25; p < 0.05). The results demonstrated that the health status of participants was a significant modifier of pooled correlations. In addition, the personal to ambient (P/A) ratio for PM 2.5 and average ambient BC/EC levels were potential effect moderators of the pooled ṝ. The funnel plots and Egger's regression test indicated inevident publication bias. The pooled estimates were robust through sensitivity analyses. The results support the growing consensus that the validity coefficient of proxy measures should be addressed when interpreting results from epidemiological studies to better understand how strong health outcomes are affected by different levels of PM 2.5 and their components., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Characterizing how variation in the tempo and mode of evolution has structured the phenotypic diversity of extant species is a central goal of macroevolution 1-3 . However, studies are typically limited to a handful of traits 4-6 , providing incomplete information. We analyse morphological diversification in living birds, an ecologically diverse group 7 , documenting structural scales from 'pan-skeletal' proportions down to the localized three-dimensional shape changes of individual bones. We find substantial variation in evolutionary modes among avian subgroups and among skeletal parts, indicating widespread mosaicism and possible differences in the structure of the macroevolutionary landscape across Earth's main environments. Water-linked groups, especially Aequorlitornithes (waterbirds), have repeatedly explored a large portion of their total morphospace, emphasizing variation in body proportions and in the shape of bones close to the body core, which are functionally related to the mechanics of locomotion 8 . By contrast, landbirds (Inopinaves) evolved distinct, group-specific body forms early in the aftermath of the K-Pg and subsequently emphasized local shape variation, especially in the head and distal limb bones, which interact more directly with the environment. Passerines, which comprise more than half of all bird species, show a conservative evolutionary dynamic that resulted in low disparity across all skeletal parts. Evidence for early establishment of the morphospace of living birds is clear for some skeletal parts, including beaks and the combined skeletal morphology. However, we find little evidence for early partitioning of that morphospace, contrary to more specific predictions of 'niche-filling' models 1,9 . Nevertheless, early divergence among broad environmental types may have caused an early divergence of evolutionary modes, suggesting an important role for environmental divergence in structuring the radiation of crown-group birds., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Glacier meltwater supplies silicon (Si) and iron (Fe) sourced from weathered bedrock to downstream ecosystems. However, the extent to which these nutrients reach the ocean is regulated by the nature of the benthic cycling of dissolved Si and Fe within fjord systems, given the rapid deposition of reactive particulate fractions at fjord heads. Here, we examine the benthic cycling of the two nutrients at four Patagonian fjord heads through geochemical analyses of sediment pore waters, including Si and Fe isotopes (δ 30 Si and δ 56 Fe), and reaction-transport modeling for Si. A high diffusive flux of dissolved Fe from the fjord sediments (up to 0.02 mmol m -2  day -1 ) compared to open ocean sediments (typically <0.001 mmol m -2  day -1 ) is supported by both reductive and non-reductive dissolution of glacially-sourced reactive Fe phases, as reflected by the range of pore water δ 56 Fe (-2.7 to +0.8‰). In contrast, the diffusive flux of dissolved Si from the fjord sediments (0.02-0.05 mmol m -2  day -1 ) is relatively low (typical ocean values are >0.1 mmol m -2  day -1 ). High pore water δ 30 Si (up to +3.3‰) observed near the Fe(II)-Fe(III) redox boundary is likely associated with the removal of dissolved Si by Fe(III) mineral phases, which, together with high sedimentation rates, contribute to the low diffusive flux of Si at the sampled sites. Our results suggest that early diagenesis promotes the release of dissolved Fe, yet suppresses the release of dissolved Si at glaciated fjord heads, which has significant implications for understanding the downstream transport of these nutrients along fjord systems., Competing Interests: The authors declare no conflicts of interest relevant to this study., (© 2022. The Authors.)

High-entropy alloys are solid solutions of multiple principal elements that are capable of reaching composition and property regimes inaccessible for dilute materials. Discovering those with valuable properties, however, too often relies on serendipity, because thermodynamic alloy design rules alone often fail in high-dimensional composition spaces. We propose an active learning strategy to accelerate the design of high-entropy Invar alloys in a practically infinite compositional space based on very sparse data. Our approach works as a closed-loop, integrating machine learning with density-functional theory, thermodynamic calculations, and experiments. After processing and characterizing 17 new alloys out of millions of possible compositions, we identified two high-entropy Invar alloys with extremely low thermal expansion coefficients around 2 × 10 -6 per degree kelvin at 300 kelvin. We believe this to be a suitable pathway for the fast and automated discovery of high-entropy alloys with optimal thermal, magnetic, and electrical properties.

The Irrawaddy (Ayeyarwaddy) and Salween (Thanlwin) globally rank among the largest rivers for supplying dissolved and particulate material to the ocean. Along with the Sittaung and Kaladan rivers they have societal importance to Myanmar in terms water sources and food production. Despite their importance for global biogeochemical cycles and the ~50 million people who live in their catchments, the chemistry of these rivers is poorly known. This study presents a comprehensive survey of dissolved (<0.22 μm) trace element concentrations (Sr, Fe, Al, Ba, Mn, V, Rb, Cu, Zn, As, Li, Ni, Mo, Cr, U, Pb, Sb, Co, Cs, Tl and Cd) at 38 locations within these river catchments, spanning a period of 2 years. The results highlight the global importance of the Irrawaddy and Salween rivers for trace element global biogeochemical cycles; contributing between 1 and 17 % of global dissolved riverine fluxes to the land-ocean interface for the studied elements. Area normalized dissolved fluxes in these catchments are ~2 to 10 times higher than global average values for most elements, consistent with high rates of chemical weathering. In general, anthropogenic activities have yet to significantly perturb dissolved trace element fluxes in these river systems. The presented dataset should therefore serve as a useful 'natural' baseline, against which future perturbations driven by climate change and/or the development of Myanmar's mining industry could be assessed. Exceptions to this include As in the Sittaung River and Sb, Zn, Pb and As in the Salween River, which may already be significantly impacted by anthropogenic inputs. The former represents a water quality issue of concern for public health, and so constraining the exact sources of As in the Sittaung River should be considered a priority for future research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The geological units on the floor of Jezero crater, Mars, are part of a wider regional stratigraphy of olivine-rich rocks, which extends well beyond the crater. We investigated the petrology of olivine and carbonate-bearing rocks of the Séítah formation in the floor of Jezero. Using multispectral images and x-ray fluorescence data, acquired by the Perseverance rover, we performed a petrographic analysis of the Bastide and Brac outcrops within this unit. We found that these outcrops are composed of igneous rock, moderately altered by aqueous fluid. The igneous rocks are mainly made of coarse-grained olivine, similar to some martian meteorites. We interpret them as an olivine cumulate, formed by settling and enrichment of olivine through multistage cooling of a thick magma body.

The Perseverance rover landed in Jezero crater, Mars, to investigate ancient lake and river deposits. We report observations of the crater floor, below the crater's sedimentary delta, finding that the floor consists of igneous rocks altered by water. The lowest exposed unit, informally named Séítah, is a coarsely crystalline olivine-rich rock, which accumulated at the base of a magma body. Magnesium-iron carbonates along grain boundaries indicate reactions with carbon dioxide-rich water under water-poor conditions. Overlying Séítah is a unit informally named Máaz, which we interpret as lava flows or the chemical complement to Séítah in a layered igneous body. Voids in these rocks contain sulfates and perchlorates, likely introduced by later near-surface brine evaporation. Core samples of these rocks have been stored aboard Perseverance for potential return to Earth.

Among terrestrial vertebrates, only crown birds (Neornithes) rival mammals in terms of relative brain size and behavioural complexity. Relatedly, the anatomy of the avian central nervous system and associated sensory structures, such as the vestibular system of the inner ear, are highly modified with respect to those of other extant reptile lineages. However, a dearth of three-dimensional Mesozoic fossils has limited our knowledge of the origins of the distinctive endocranial structures of crown birds. Traits such as an expanded, flexed brain, a ventral connection between the brain and spinal column, and a modified vestibular system have been regarded as exclusive to Neornithes. Here, we demonstrate all of these 'advanced' traits in an undistorted braincase from an Upper Cretaceous enantiornithine bonebed in southeastern Brazil. Our discovery suggests that these crown bird-like endocranial traits may have originated prior to the split between Enantiornithes and the more crownward portion of avian phylogeny over 140 Ma, while coexisting with a remarkably plesiomorphic cranial base and posterior palate region. Altogether, our results support the interpretation that the distinctive endocranial morphologies of crown birds and their Mesozoic relatives are affected by complex trade-offs between spatial constraints during development.

The number of zeolitic imidazolate frameworks (ZIFs) that form melt-quenched glasses remains limited, with most displaying the cag network topology. Here, we expand our studies to zni topology ZIFs, starting with ZIF-zni [Zn(Im) 2 ] before changing its linker chemistry, by incorporating 2-methylimidazolate and 5-aminobenzimidazolate. ZIF-zni was found to melt and form a glass, with T m = 322 °C, although it was not possible to prepare the glass without zinc oxide impurities. The addition of 2-methylimidazolate to the structure gave ZIF-61 [Zn(Im) T g ], which decomposed without passing through the liquid state. However, incorporating small quantities of 5-aminobenzimidazolate resulted in a ZIF [Zn(Im) 1.35 (mIm) 0.65 ], which decomposed without passing through the liquid state. However, incorporating small quantities of 5-aminobenzimidazolate resulted in a ZIF [Zn(Im) 1.995 = 569 °C) than pure ZIF-zni, and no evidence of zinc oxide growth. This demonstrates the sensitivity of melting behaviour in ZIFs towards linker chemistry, with only a 0.25% variation capable of eliciting a 7 °C change in melting temperature. This study highlights the chemical sensitivity of melting in ZIFs and serves as a promising strategy for tuning their melting behaviour.0.005 ] with a lower melting temperature ( T m = 569 °C) than pure ZIF-zni, and no evidence of zinc oxide growth. This demonstrates the sensitivity of melting behaviour in ZIFs towards linker chemistry, with only a 0.25% variation capable of eliciting a 7 °C change in melting temperature. This study highlights the chemical sensitivity of melting in ZIFs and serves as a promising strategy for tuning their melting behaviour.

Recent thermodynamic and experimental studies have suggested that volatile organic compounds (e.g., methane, formate, and acetate) can be produced and stabilized in subduction zones, potentially playing an important role in the deep carbon cycle. However, field evidence for the high-pressure production and storage of solid organic compounds is missing. Here, we examine forearc serpentinite clasts recovered by drilling mud volcanoes above the Mariana subduction zone. Notable correlations between carbon and iron stable-isotope signatures and fluid-mobile element (B, As and Sb) concentrations provide evidence for the percolation of slab-derived CO 2 -rich aqueous fluids through the forearc mantle. The presence of carbonaceous matter rich in aliphatic moieties within high-temperature clasts (>350°C) demonstrates that molecular hydrogen production associated with forearc serpentinization is an efficient mechanism for the reduction and conversion of slab-derived CO 2 -rich fluids into solid organic compounds. These findings emphasize the need to consider the forearc mantle as an important reservoir of organic carbon on Earth.

Prebiotic systems chemistry suggests that high phosphate concentrations were necessary to synthesise molecular building blocks and sustain primitive cellular systems. However, current understanding of mineral solubility predicts negligible phosphate concentrations for most natural waters, yet the role of Fe 2+ , ubiquitous on early Earth, is poorly quantified. Here we determine the solubility of Fe(II)-phosphate in synthetic seawater as a function of pH and ionic strength, integrate these observations into a thermodynamic model that predicts phosphate concentrations across a range of aquatic conditions, and validate these predictions against modern anoxic sediment pore waters. Experiments and models show that Fe 2+ significantly increases the solubility of all phosphate minerals in anoxic systems, suggesting that Hadean and Archean seawater featured phosphate concentrations ~10 3 -10 4 times higher than currently estimated. This suggests that seawater readily met the phosphorus requirements of emergent cellular systems and early microbial life, perhaps fueling primary production during the advent of oxygenic photosynthesis., (© 2022. The Author(s).)

The tropical West Pacific hosts the warmest part of the surface ocean and has a considerable impact on the global climate system. Reconstructions of past temperature in this region can elucidate climate connections between the tropics and poles and the sensitivity of tropical temperature to greenhouse forcing. However, existing data are equivocal and reliable information from terrestrial archives is particularly sparse. Here we constrain the magnitude and timing of land temperature change in the tropical West Pacific across the last deglaciation using an exceptionally precise paleothermometer applied to a well-dated stalagmite from Northern Borneo. We show that the cave temperature increased by 4.4 ± 0.3 °C (2 SEM) from the Last Glacial Maximum to the Holocene, amounting to 3.6 ± 0.3 °C (2 SEM) when correcting for sea-level induced cave altitude change. The warming closely follows atmospheric CO 2 and Southern Hemisphere warming. This contrasts with hydroclimate, as reflected by drip water δ 18 O, which responds to Northern Hemisphere cooling events in the form of prominent drying, while temperature was rising. Our results thus show a close response of tropical temperature to greenhouse forcing, independent of shifts in the tropical circulation patterns., (© 2022. The Author(s).)

Recent Icelandic rifting events have illuminated the roles of centralized crustal magma reservoirs and lateral magma transport 1-4 , important characteristics of mid-ocean ridge magmatism 1,5 . A consequence of such shallow crustal processing of magmas 4,5 is the overprinting of signatures that trace the origin, evolution and transport of melts in the uppermost mantle and lowermost crust 6,7 . Here we present unique insights into processes occurring in this zone from integrated petrologic and geochemical studies of the 2021 Fagradalsfjall eruption on the Reykjanes Peninsula in Iceland. Geochemical analyses of basalts erupted during the first 50 days of the eruption, combined with associated gas emissions, reveal direct sourcing from a near-Moho magma storage zone. Geochemical proxies, which signify different mantle compositions and melting conditions, changed at a rate unparalleled for individual basaltic eruptions globally. Initially, the erupted lava was dominated by melts sourced from the shallowest mantle but over the following three weeks became increasingly dominated by magmas generated at a greater depth. This exceptionally rapid trend in erupted compositions provides an unprecedented temporal record of magma mixing that filters the mantle signal, consistent with processing in near-Moho melt lenses containing 10 7 -10 8  m 3 of basaltic magma. Exposing previously inaccessible parts of this key magma processing zone to near-real-time investigations provides new insights into the timescales and operational mode of basaltic magma systems., (© 2022. The Author(s).)

Ferroic domain dynamics, as a function of external stimuli, can be collectively described as scale-invariant avalanches characterised by a critical exponent that are sensitive to the complexity of the domain microstructure. The understanding and manipulation of these avalanches lies at the heart of developing novel applications such as neuromorphic computing. Here we combine in situ heating optical observations and mean-field analysis to investigate the collective domain behaviour in pure-ferroelastic lanthanum aluminate (LaAlO[Formula: see text]) as a function of aspect ratio, the ratio of sample length to width, where the movement of the domains is predominantly driven by thermal stresses via thermal expansion/contraction during heat cycling. Our observations demonstrate that the aspect ratio induces (1) distinctive domain microstructures at room temperature, (2) a deviation of dynamical behaviour at high temperatures and (3) critical exponent mixing in the higher aspect ratio samples that accompanies this behaviour. While the critical exponents of each aspect ratio fall within mean-field predicted values, we highlight the effect that the aspect ratio has in inducing exponent mixing. Hence, furthering our understanding towards tuning and controlling avalanches which is crucial for fundamental and applied research., (© 2022. The Author(s).)

By contrast to many previously enigmatic Palaeozoic fossils, the Carboniferous metazoan Typhloesus has defied phylogenetic placement. Here, we document new features, including possible phosphatized muscle tissues and a hitherto unrecognized feeding apparatus with two sets of ca 20 spinose teeth whose closest similarities appear to lie with the molluscan radula. The ribbon-like structure, located well behind the mouth area and deep into the anterior part of the body, is interpreted as being in an inverted proboscis configuration. Gut contents, mostly conodonts, in the midgut area demonstrate that Typhloesus was an active predator. This animal was capable of propelling itself in the water column using its flexible body and a prominent posterior fin. The affinity of Typhloesus as a pelagic mollusc remains problematic but may lie more closely with the gastropods. Heteropod gastropods share with Typhloesus an active predatory lifestyle and have a comparable general body organization, albeit they possess characteristic aragonitic shells and their origins in the Jurassic post-date Typhloesus . Typhloesus may represent an independent radiation of Mid-Palaeozoic pelagic gastropods.

Dissolved oxygen (O 2 ) is essential for most ocean ecosystems, fuelling organisms' respiration and facilitating the cycling of carbon and nutrients. Oxygen measurements have been interpreted to indicate that the ocean's oxygen-deficient zones (ODZs) are expanding under global warming 1,2 . However, models provide an unclear picture of future ODZ change in both the near term and the long term 3-6 . The paleoclimate record can help explore the possible range of ODZ changes in warmer-than-modern periods. Here we use foraminifera-bound nitrogen (N) isotopes to show that water-column denitrification in the eastern tropical North Pacific was greatly reduced during the Middle Miocene Climatic Optimum (MMCO) and the Early Eocene Climatic Optimum (EECO). Because denitrification is restricted to oxygen-poor waters, our results indicate that, in these two Cenozoic periods of sustained warmth, ODZs were contracted, not expanded. ODZ contraction may have arisen from a decrease in upwelling-fuelled biological productivity in the tropical Pacific, which would have reduced oxygen demand in the subsurface. Alternatively, invigoration of deep-water ventilation by the Southern Ocean may have weakened the ocean's 'biological carbon pump', which would have increased deep-ocean oxygen. The mechanism at play would have determined whether the ODZ contractions occurred in step with the warming or took centuries or millennia to develop. Thus, although our results from the Cenozoic do not necessarily apply to the near-term future, they might imply that global warming may eventually cause ODZ contraction., (© 2022. The Author(s).)

The invasion of the land was a complex, protracted process, punctuated by mass extinctions, that involved multiple routes from marine environments. We integrate paleobiology, ichnology, sedimentology, and geomorphology to reconstruct Paleozoic terrestrialization. Cambrian landscapes were dominated by laterally mobile rivers with unstable banks in the absence of significant vegetation. Temporary incursions by arthropods and worm-like organisms into coastal environments apparently did not result in establishment of continental communities. Contemporaneous lacustrine faunas may have been inhibited by limited nutrient delivery and high sediment loads. The Ordovician appearance of early land plants triggered a shift in the primary locus of the global clay mineral factory, increasing the amount of mudrock on the continents. The Silurian-Devonian rise of vascular land plants, including the first forests and extensive root systems, was instrumental in further retaining fine sediment on alluvial plains. These innovations led to increased architectural complexity of braided and meandering rivers. Landscape changes were synchronous with establishment of freshwater and terrestrial arthropod faunas in overbank areas, abandoned fluvial channels, lake margins, ephemeral lakes, and inland deserts. Silurian-Devonian lakes experienced improved nutrient availability, due to increased phosphate weathering and terrestrial humic matter. All these changes favoured frequent invasions to permament establishment of jawless and jawed fishes in freshwater habitats and the subsequent tetrapod colonization of the land. The Carboniferous saw rapid diversification of tetrapods, mostly linked to aquatic reproduction, and land plants, including gymnosperms. Deeper root systems promoted further riverbank stabilization, contributing to the rise of anabranching rivers and braided systems with vegetated islands. New lineages of aquatic insects developed and expanded novel feeding modes, including herbivory. Late Paleozoic soils commonly contain pervasive root and millipede traces. Lacustrine animal communities diversified, accompanied by increased food-web complexity and improved food delivery which may have favored permanent colonization of offshore and deep-water lake environments. These trends continued in the Permian, but progressive aridification favored formation of hypersaline lakes, which were stressful for colonization. The Capitanian and end-Permian extinctions affected lacustrine and fluvial biotas, particularly the invertebrate infauna, although burrowing may have allowed some tetrapods to survive associated global warming and increased aridification., (© The Author(s) 2022. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology.)

The origin of amniotes 320 million years ago signaled independence from water in vertebrates and was closely followed by divergences within the mammal and reptile stem lineages (Synapsida and Reptilia). Early members of both groups had highly similar morphologies, being superficially "lizard-like" forms with many plesiomorphies. However, the extent to which they might have exhibited divergent patterns of evolutionary change, with the potential to explain the large biological differences between their living members, is unresolved. We use a new, comprehensive phylogenetic dataset to quantify variation in rates and constraints of morphological evolution among Carboniferous-early Permian amniotes. We find evidence for an early burst of evolutionary rates, resulting in the early origins of morphologically distinctive subgroups that mostly persisted through the Cisuralian. Rates declined substantially through time, especially in reptiles. Early reptile evolution was also more constrained compared with early synapsids, exploring a more limited character state space. Postcranial innovation in particular was important in early synapsids, potentially related to their early origins of large body size. In contrast, early reptiles predominantly varied the temporal region, suggesting disparity in skull and jaw kinematics, and foreshadowing the variability of cranial biomechanics seen in reptiles today. Our results demonstrate that synapsids and reptiles underwent an early divergence of macroevolutionary patterns. This laid the foundation for subsequent evolutionary events and may be critical in understanding the substantial differences between mammals and reptiles today. Potential explanations include an early divergence of developmental processes or of ecological factors, warranting cross-disciplinary investigation. [Amniote; body size; constraint; phylogeny; rate.]., (© The Author(s) 2022. Published by Oxford University Press on behalf of the Society of Systematic Biologists.)

Cnidarians are a disparate and ancient phylum, encompassing corals and jellyfish, and occupy both the pelagic and benthic realms. They have a rich fossil record from the Phanerozoic eon lending insight into the early history of the group but, although cnidarians diverged from other animals in the Precambrian period, their record from the Ediacaran period (635-542 million years ago) is controversial. Here, we describe a new fossil cnidarian-Auroralumina attenboroughii gen. et sp. nov.-from the Ediacaran of Charnwood Forest (557-562 million years ago) that shows two bifurcating polyps enclosed in a rigid, polyhedral, organic skeleton with evidence of simple, densely packed tentacles. Auroralumina displays a suite of characters allying it to early medusozoans but shows others more typical of Anthozoa. Phylogenetic analyses recover Auroralumina as a stem-group medusozoan and, therefore, the oldest crown-group cnidarian. Auroralumina demonstrates both the establishment of the crown group of an animal phylum and the fixation of its body plan tens of millions of years before the Cambrian diversification of animal life., (© 2022. The Author(s).)

Anthropogenic carbon emissions are causing seawater pH to decline, yet the impact on marine calcifiers is uncertain. Scleractinian corals and coralline algae strongly elevate the pH of their calcifying fluid (CF) to promote calcification. Other organisms adopt less energetically demanding calcification approaches but restrict their habitat. Stylasterid corals occur widely (extending well below the carbonate saturation horizon) and precipitate both aragonite and high-Mg calcite, however, their mode of biocalcification and resilience to ocean acidification are unknown. Here we measure skeletal boron isotopes (δ 11 B), B/Ca, and U/Ca to provide the first assessment of pH and rate of seawater flushing of stylasterid CF. Remarkably, both aragonitic and high-Mg calcitic stylasterids have low δ 11 B values implying little modification of internal pH. Collectively, our results suggest stylasterids have low seawater exchange rates into the calcifying space or rely on organic molecule templating to facilitate calcification. Thus, despite occupying similar niches to Scleractinia, Stylasteridae exhibit highly contrasting biocalcification, calling into question their resilience to ocean acidification., (© 2022. The Author(s).)

The postcranial skeleton of Australopithecus afarensis (AL 288-1) exhibits clear adaptations for bipedality, although there is some debate as to the efficiency and frequency of such upright movement. Some researchers argue that AL 288-1 walked with an erect limb like modern humans do, whilst others advocate for a "bent-hip bent-knee" (BHBK) gait, although in recent years the general consensus favors erect bipedalism. To date, no quantitative method has addressed the articulation of the AL 288-1 hip joint, nor its range of motion (ROM) with consideration for joint spacing, used as a proxy for the thickness of the articular cartilage present within the joint spacing which can affect how a joint moves. Here, we employed ROM mapping methods to estimate the joint spacing of AL 288-1's hip joint in comparison to a modern human and chimpanzee. Nine simulations assessed different joint spacing and tested the range of joint congruency (i.e., ranging from a closely packed socket to loosely packed). We further evaluated the sphericity of the femoral head and whether three rotational degrees of freedom (DOFs) sufficiently captures the full ROM or if translational DOFs must be included. With both setups, we found that the AL 288-1 hip was unlikely to be highly congruent (as it is in modern humans) because this would severely restrict hip rotational movement and would severely limit the capability for both bipedality and even arboreal locomotion. Rather, the hip was more cartilaginous than it is in the modern humans, permitting the hip to rotate into positions necessitated by both terrestrial and arboreal movements. Rotational-only simulations found that AL 288-1 was unable to extend the hip like modern humans, forcing the specimen to employ a BHBK style of walking, thus contradicting 40+ years of previous research into the locomotory capabilities of AL 288-1. Therefore, we advocate that differences in the sphericity of the AL 288-1 femoral head with that of a modern human necessitates all six DOFs to be included in which AL 288-1 could osteologically extend the hip to facilitate a human-like gait., (© The Author(s) 2022. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology.)

The influence of climate change on civil conflict and societal instability in the premodern world is a subject of much debate, in part because of the limited temporal or disciplinary scope of case studies. We present a transdisciplinary case study that combines archeological, historical, and paleoclimate datasets to explore the dynamic, shifting relationships among climate change, civil conflict, and political collapse at Mayapan, the largest Postclassic Maya capital of the Yucatán Peninsula in the thirteenth and fourteenth centuries CE. Multiple data sources indicate that civil conflict increased significantly and generalized linear modeling correlates strife in the city with drought conditions between 1400 and 1450 cal. CE. We argue that prolonged drought escalated rival factional tensions, but subsequent adaptations reveal regional-scale resiliency, ensuring that Maya political and economic structures endured until European contact in the early sixteenth century CE., (© 2022. The Author(s).)

Materials that sustain localized surface plasmon resonances have a broad technology potential as attractive platforms for surface-enhanced spectroscopies, chemical and biological sensing, light-driven catalysis, hyperthermal cancer therapy, waveguides, and so on. Most plasmonic nanoparticles studied to date are composed of either Ag or Au, for which a vast array of synthetic approaches are available, leading to controllable size and shape. However, recently, alternative materials capable of generating plasmonically enhanced light-matter interactions have gained prominence, notably Cu, Al, In, and Mg. In this Perspective, we give an overview of the attributes of plasmonic nanostructures that lead to their potential use and how their performance is dictated by the choice of plasmonic material, emphasizing the similarities and differences between traditional and emerging plasmonic compositions. First, we discuss the materials limitation encapsulated by the dielectric function. Then, we evaluate how size and shape maneuver localized surface plasmon resonance (LSPR) energy and field distribution and address how this impacts applications. Next, biocompatibility, reactivity, and cost, all key differences underlying the potential of non-noble metals, are highlighted. We find that metals beyond Ag and Au are of competitive plasmonic quality. We argue that by thinking outside of the box, i.e., by looking at nonconventional materials such as Mg, one can broaden the frequency range and, more importantly, combine the plasmonic response with other properties essential for the implementation of plasmonic technologies., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The external surface microornament of the glass scallops Catillopecten natalyae and malyutinae is made by calcitic spiny projections consisting of a stem that later divides into three equally spaced and inclined branches (here called aerials). C. natalyae contains larger and smaller aerials, whereas C. malyutinae only secreted aerials of the second type. A remarkable feature is that aerials within each type are fairly similar in size and shape and highly co-oriented, thus constituting a most sophisticated microornament. We demonstrate that aerials are single crystals whose morphology is strongly controlled by the crystallography, with the stem being parallel to the c-axis of calcite, and the branches extending along the edges of the {104} calcite rhombohedron. They grow epitaxially onto the foliated prisms of the outer shell layer. The co-orientation of the prisms explains that of the aerials. We have developed a model in which every aerial grows within a periostracal pouch. When this pouch reaches the growth margin, the mantle initiates the production of the aerial. Nevertheless, later growth of the aerial is remote, i.e. far from the contact with the mantle. We show how such an extremely sophisticated microornament has a morphology and co-orientation which are determined by crystal growth., (© 2022. The Author(s).)

The hypersaline Dead Sea and its sediments are natural laboratories for studying extremophile microorganism habitat response to environmental change. In modern times, increased freshwater runoff to the lake surface waters resulted in stratification and dilution of the upper water column followed by microbial blooms. However, whether these events facilitated a microbial response in the deep lake and sediments is obscure. Here we investigate archived evidence of microbial processes and changing regional hydroclimate conditions by reconstructing deep Dead Sea chemical compositions from pore fluid major ion concentration and stable S, O, and C isotopes, together with lipid biomarkers preserved in the hypersaline deep Dead Sea ICDP-drilled core sediments dating to the early Holocene (ca. 10,000 years BP). Following a significant negative lake water balance resulting in salt layer deposits at the start of the Holocene, there was a general period of positive net water balance at 9500-8300 years BP. The pore fluid isotopic composition of sulfate exhibit evidence of intensified microbial sulfate reduction, where both δ 34 S and δ 18 O of sulfate show a sharp increase from estimated base values of 15.0‰ and 13.9‰ to 40.2‰ and 20.4‰, respectively, and a δ 34 S vs. δ 18 O slope of 0.26. The presence of the n-C 17 alkane biomarker in the sediments suggests an increase of cyanobacteria or phytoplankton contribution to the bulk organic matter that reached the deepest parts of the Dead Sea. Although hydrologically disconnected, both the Mediterranean Sea and the Dead Sea microbial ecosystems responded to increased freshwater runoff during the early Holocene, with the former depositing the organic-rich sapropel 1 layer due to anoxic water column conditions. In the Dead Sea prolonged positive net water balance facilitated primary production and algal blooms in the upper waters and intensified microbial sulfate reduction in the hypolimnion and/or at the sediment-brine interface., (© 2022 The Authors. Geobiology published by John Wiley & Sons Ltd.)

Trophic position is a fundamental characteristic of animals, yet it is unknown in many extinct species. In this study, we ground-truth the 15 N/ 14 N ratio of enameloid-bound organic matter (δ 15 N EB ) as a trophic level proxy by comparison to dentin collagen δ 15 N and apply this method to the fossil record to reconstruct the trophic level of the megatooth sharks (genus Otodus ). These sharks evolved in the Cenozoic, culminating in Otodus megalodon , a shark with a maximum body size of more than 15 m, which went extinct 3.5 million years ago. Very high δ 15 N EB values (22.9 ± 4.4‰) of O. megalodon from the Miocene and Pliocene show that it occupied a higher trophic level than is known for any marine species, extinct or extant. δ 15 N EB also indicates a dietary shift in sharks of the megatooth lineage as they evolved toward the gigantic O. megalodon , with the highest trophic level apparently reached earlier than peak size.

In the wake of rapid CO 2 release tied to the emplacement of the Siberian Traps, elevated temperatures were maintained for over five million years during the end-Permian biotic crisis. This protracted recovery defies our current understanding of climate regulation via the silicate weathering feedback, and hints at a fundamentally altered carbon and silica cycle. Here, we propose that the development of widespread marine anoxia and Si-rich conditions, linked to the collapse of the biological silica factory, warming, and increased weathering, was capable of trapping Earth's system within a hyperthermal by enhancing ocean-atmosphere CO 2 recycling via authigenic clay formation. While solid-Earth degassing may have acted as a trigger, subsequent biotic feedbacks likely exacerbated and prolonged the environmental crisis. This refined view of the carbon-silica cycle highlights that the ecological success of siliceous organisms exerts a potentially significant influence on Earth's climate regime., (© 2022. The Author(s).)

Life in the clouds of Venus, if present in sufficiently high abundance, must be affecting the atmospheric chemistry. It has been proposed that abundant Venusian life could obtain energy from its environment using three possible sulfur energy-metabolisms. These metabolisms raise the possibility of Venus's enigmatic cloud-layer SO 2 -depletion being caused by life. We here couple each proposed energy-metabolism to a photochemical-kinetics code and self-consistently predict the composition of Venus's atmosphere under the scenario that life produces the observed SO 2 -depletion. Using this photo-bio-chemical kinetics code, we show that all three metabolisms can produce SO 2 -depletions, but do so by violating other observational constraints on Venus's atmospheric chemistry. We calculate the maximum possible biomass density of sulfur-metabolising life in the clouds, before violating observational constraints, to be ~10 -5  - 10 -3  mg m -3 . The methods employed are equally applicable to aerial biospheres on Venus-like exoplanets, planets that are optimally poised for atmospheric characterisation in the near future., (© 2022. The Author(s).)

Long-term exposure to ambient ozone (O 3 ) can lead to a series of chronic diseases and associated premature deaths, and thus population-level environmental health studies hanker after the high-resolution surface O 3 concentration database. In response to this demand, we innovatively construct a space-time Bayesian neural network parametric regressor to fuse TOAR historical observations, CMIP6 multimodel simulation ensemble, population distributions, land cover properties, and emission inventories altogether and downscale to 10 km × 10 km spatial resolution with high methodological reliability ( R 2 = 0.89-0.97, RMSE = 1.97-3.42 ppbV), fair prediction accuracy ( R 2 are 15.1±7.4 ppbV higher than urban globally averaged across 30 historical years during 1990-2019, with developing countries being of the most evident differences. The globe-wide urban surface O R 2 tend to be relatively stable, except for the rising tendencies in China and India. Using CMIP6 model simulations directly without urban-rural differentiation will lead to underestimations of population O 3 exposure by 2.0±0.8 ppbV averaged over each historical year. Our original Bayesian neural network framework contributes to the deep-learning-driven environmental studies methodologically by providing a brand-new feasible way to realize data fusion and downscaling, which maintains high interpretability by conforming to the principles of spatial statistics without compromising the prediction accuracy. Moreover, the 30-year highly spatial resolved monthly surface O 3 are climbing by 1.9±2.3 ppbV per decade, except for the decreasing trends in eastern United States. On the other hand, the global rural surface O 3 tend to be relatively stable, except for the rising tendencies in China and India. Using CMIP6 model simulations directly without urban-rural differentiation will lead to underestimations of population O 3 exposure by 2.0±0.8 ppbV averaged over each historical year. Our original Bayesian neural network framework contributes to the deep-learning-driven environmental studies methodologically by providing a brand-new feasible way to realize data fusion and downscaling, which maintains high interpretability by conforming to the principles of spatial statistics without compromising the prediction accuracy. Moreover, the 30-year highly spatial resolved monthly surface O 3 database with multiple metrics fills in the literature gap for long-term surface O 3 exposure tracing.

Archosauria diversified throughout the Triassic Period before experiencing two mass extinctions near its end ∼201 Mya, leaving only the crocodile-lineage (Crocodylomorpha) and bird-lineage (Dinosauria) as survivors; along with the pterosaurian flying reptiles. About 50 years ago, the "locomotor superiority hypothesis" (LSH) proposed that dinosaurs ultimately dominated by the Early Jurassic Period because their locomotion was superior to other archosaurs'. This idea has been debated continuously since, with taxonomic and morphological analyses suggesting dinosaurs were "lucky" rather than surviving due to being biologically superior. However, the LSH has never been tested biomechanically. Here we present integration of experimental data from locomotion in extant archosaurs with inverse and predictive simulations of the same behaviours using musculoskeletal models, showing that we can reliably predict how extant archosaurs walk, run and jump. These simulations have been guiding predictive simulations of extinct archosaurs to estimate how they moved, and we show our progress in that endeavour. The musculoskeletal models used in these simulations can also be used for simpler analyses of form and function such as muscle moment arms, which inform us about more basic biomechanical similarities and differences between archosaurs. Placing all these data into an evolutionary and biomechanical context, we take a fresh look at the LSH as part of a critical review of competing hypotheses for why dinosaurs (and a few other archosaur clades) survived the Late Triassic extinctions. Early dinosaurs had some quantifiable differences in locomotor function and performance vs. some other archosaurs, but other derived dinosaurian features (e.g., metabolic or growth rates, ventilatory abilities) are not necessarily mutually exclusive from the LSH; or maybe even an opportunistic replacement hypothesis; in explaining dinosaurs' success., (© The Author(s) 2022. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology.)

The lowermost mantle right above the core-mantle boundary is highly heterogeneous containing multiple poorly understood seismic features. The smallest but most extreme heterogeneities yet observed are 'Ultra-Low Velocity Zones' (ULVZ). We exploit seismic shear waves that diffract along the core-mantle boundary to provide new insight into these enigmatic structures. We measure a rare core-diffracted signal refracted by a ULVZ at the base of the Hawaiian mantle plume at unprecedentedly high frequencies. This signal shows remarkably longer time delays at higher compared to lower frequencies, indicating a pronounced internal variability inside the ULVZ. Utilizing the latest computational advances in 3D waveform modeling, here we show that we are able to model this high-frequency signal and constrain high-resolution ULVZ structure on the scale of kilometers, for the first time. This new observation suggests a chemically distinct ULVZ with increasing iron content towards the core-mantle boundary, which has implications for Earth's early evolutionary history and core-mantle interaction., (© 2022. The Author(s).)

The reduction of 4-nitrophenol (4-NiP) to 4-aminophenol (4-AP) with an excess of sodium borohydride is commonly used as a model reaction to assess the catalytic activity of metallic nanoparticles. This reaction is considered both a potentially important step in industrial water treatment and an attractive, commercially relevant synthetic pathway. Surprisingly, an important factor, the role of the reaction medium on the reduction performance, has so far been overlooked. Here, we report a pronounced effect of the solvent on the reaction kinetics in the presence of silver and gold nanoparticles. We demonstrate that the addition of methanol, ethanol, or isopropanol to the reaction mixture leads to a dramatic decrease in the reaction rate. For typical concentrations of reactants, the reduction is completely suppressed in the presence of 50 vol% alcohols. 4-NiP reduction rate in aqueous alcohol mixtures can, however, be improved noticeably by increasing the borohydride concentration or the reaction temperature. The analysis of various factors responsible for solvent effects reveals that the decrease in the reduction rate in the presence of alcohols is related, amongst others, to a substantially higher oxygen solubility in alcohols compared to water. The results of this work show that the effects of solvent properties on reaction kinetics must be considered for unambiguous comparison and optimization of the catalytic performance of metallic nanoparticles in the liquid phase 4-NiP reduction., Competing Interests: The authors report no competing interests., (This journal is © The Royal Society of Chemistry.)

Long-term ozone (O 3 ) exposure may lead to non-communicable diseases and increase mortality risk. However, cohort-based studies are relatively rare, and inconsistent exposure metrics impair the credibility of epidemiological evidence synthetization. To provide more accurate meta-estimations, this study updates existing systematic reviews by including recent studies and summarizing the quantitative associations between O 3 exposure and cause-specific mortality risks, based on unified exposure metrics. Cross-metric conversion factors were estimated linearly by decadal observations during 1990-2019. The Hunter-Schmidt random-effects estimator was applied to pool the relative risks. A total of 25 studies involving 226,453,067 participants (14 unique cohorts covering 99,855,611 participants) were included in the systematic review. After linearly unifying the inconsistent O 3 exposure metrics , the pooled relative risks associated with every 10 nmol mol -1 (ppbV) incremental O 3 exposure, by mean of the warm-season daily maximum 8-h average metric, were as follows: 1.014 with 95% confidence interval (CI) ranging 1.009-1.019 for all-cause mortality; 1.025 (95% CI: 1.010-1.040) for respiratory mortality; 1.056 (95% CI: 1.029-1.084) for COPD mortality; 1.019 (95% CI: 1.004-1.035) for cardiovascular mortality; and 1.074 (95% CI: 1.054-1.093) for congestive heart failure mortality. Insignificant mortality risk associations were found for ischemic heart disease, cerebrovascular diseases, and lung cancer. Adjustment for exposure metrics laid a solid foundation for multi-study meta-analysis, and widening coverage of surface O 3 observations is expected to strengthen the cross-metric conversion in the future. Ever-growing numbers of epidemiological studies supported the evidence for considerable cardiopulmonary hazards and all-cause mortality risks from long-term O 3 exposure. However, evidence of long-term O 3 exposure-associated health effects was still scarce, so more relevant studies are needed to cover more populations with regional diversity., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)

Biomechanical models and simulations of musculoskeletal function rely on accurate muscle parameters, such as muscle masses and lines of action, to estimate force production potential and moment arms. These parameters are often obtained through destructive techniques (i.e., dissection) in living taxa, frequently hindering the measurement of other relevant parameters from a single individual, thus making it necessary to combine multiple specimens and/or sources. Estimating these parameters in extinct taxa is even more challenging as soft tissues are rarely preserved in fossil taxa and the skeletal remains contain relatively little information about the size or exact path of a muscle. Here we describe a new protocol that facilitates the estimation of missing muscle parameters (i.e., muscle volume and path) for extant and extinct taxa. We created three-dimensional volumetric reconstructions for the hindlimb muscles of the extant Nile crocodile and extinct stem-archosaur Euparkeria, and the shoulder muscles of an extant gorilla to demonstrate the broad applicability of this methodology across living and extinct animal clades. Additionally, our method can be combined with surface geometry data digitally captured during dissection, thus facilitating downstream analyses. We evaluated the estimated muscle masses against physical measurements to test their accuracy in estimating missing parameters. Our estimated muscle masses generally compare favourably with segmented iodine-stained muscles and almost all fall within or close to the range of observed muscle masses, thus indicating that our estimates are reliable and the resulting lines of action calculated sufficiently accurately. This method has potential for diverse applications in evolutionary morphology and biomechanics., (© 2022. The Author(s).)

Secondary aquatic adaptations evolved independently more than 30 times from terrestrial vertebrate ancestors 1,2 . For decades, non-avian dinosaurs were believed to be an exception to this pattern. Only a few species have been hypothesized to be partly or predominantly aquatic 3-11 . However, these hypotheses remain controversial 12,13 , largely owing to the difficulty of identifying unambiguous anatomical adaptations for aquatic habits in extinct animals. Here we demonstrate that the relationship between bone density and aquatic ecologies across extant amniotes provides a reliable inference of aquatic habits in extinct species. We use this approach to evaluate the distribution of aquatic adaptations among non-avian dinosaurs. We find strong support for aquatic habits in spinosaurids, associated with a marked increase in bone density, which precedes the evolution of more conspicuous anatomical modifications, a pattern also observed in other aquatic reptiles and mammals 14-16 . Spinosaurids are revealed to be aquatic specialists with surprising ecological disparity, including subaqueous foraging behaviour in Spinosaurus and Baryonyx, and non-diving habits in Suchomimus. Adaptation to aquatic environments appeared in spinosaurids during the Early Cretaceous, following their divergence from other tetanuran theropods during the Early Jurassic 17 ., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)