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At least 109 records · Page 6

Major to trace element imaging and analysis of iron age glasses using stage scanning in the analytical dual beam microscope (tandem)

Dark and clear silicate glasses formed during an iron age vitrification event ≈ 1500 years ago at the Broborg hillfort near Uppsala, Sweden have been analyzed using a scanning electron microscope equipped with a micro-X-ray fluorescence (μXRF) spectrometer. Correlated µXRF and electron beam-induced energy dispersive spectrometry (EDS) X-ray maps were collected via stage-scanning at constant velocity. This coupled procedure represents a new approach for the cultural heritage community to conduct analytical studies of archaeometric specimens composed of metal, ceramic, or mixed inorganic/organic materials, where major and trace element compositions are registered in space for areas up to the centimeter-length scale at micrometer-scale resolution. Overview images were used to select areas for EDS beam scan maps correlated with multispectral cathodoluminescence (CL) imaging and co-located quantitative EDS and μXRF point analysis. Fe, Ca, Mg, Ti, P, Mn, Zr, Zn, and Y are enriched in the dark glass, while Si, Al, K, Na, Ba, Sr, Rb, and Ga are enriched in the clear glass. Unmelted material is comprised predominately of quartz (SiO 2 ) along with trace apatite (Ca 5 (PO 4 ) 3 [Cl,OH]) and zircon (ZrSiO 4 ). Multivariate statistical analysis was used to measure the area fractions of high variance components while lower variance components represented phase mixtures. Differences between calculated melt viscosities for the glass compositions are consistent with field and laboratory observations. Coupled large area EDS and μXRF imaging shows significant promise for informed selection of higher spatial resolution and higher sensitivity follow-up studies, e.g., those performed using synchrotron analysis.

36 MATERIALS SCIENCE↗

DEEPER: An Intergrated Platform for Deeper Roots

Crops with deeper roots would have multiple benefits, including better drought tolerance, reduced requirement for nitrogen fertilizer, and better sequestration of atmospheric CO 2 . DEEPER is an integrated platform of phenomic, genomic, and in silico technologies to generate maize lines with deeper roots. DEEPER is: LEADER (Leaf Elemental Accumulation from Deep Roots) is a breakthrough technology to nondestructively measure rooting depth by using the plant itself as a sensor. LEADER uses handheld X-ray Fluorescence spectrometry to quantify foliar accumulation of elements that are differentially distributed in the soil profile. LEADER is nondestructive and is orders of magnitude cheaper, faster, and more precise than any competing assay of rooting depth in the field. LEADER is able to distinguish deep-rooted from shallow-rooted maize lines in the field without the need for costly and noisy soil coring. RootRobot/DIRT3D, to automatically phenotype root architecture in any field, combining RootRobot, a mechatronics platform to excavate, clean, section, and image mature root crowns, with DIRT3D, software to quantify architectural traits in 3D. Anatomics, a high-throughput platform to phenotype root anatomy, combining LAT 2.0, a technology for 3D imaging of root anatomy and composition, with RootScan3D, software to automatically extract 3D anatomical and cell wall composition metrics from LAT 2.0 output. Using this platform we discovered two novel root traits, parenchyma cell wall thickness and multiseriate cortical sclerenchyma, that improve rooting depth and drought tolerance in maize and wheat. OpenSimRoot/Deep, software to simulate root interaction with hard subsoils. Using this platform we discovered novel concepts regarding how to increase crop rooting depth by modulating how individual root axes respond to hard soil. DeepGenes, a toolkit of genes, parent lines, and genomic selection strategies to enable breeding hybrids with deeper roots. We discovered 3 novel root genes that increase rooting depth in maize and wheat. DEEPER discovered novel root phenotypes for deeper rooting, and delivered validated ideotypes for deeper-rooted maize; novel technologies to rapidly assess root depth, root architecture and anatomy in field-grown plants; novel software tools for root modeling and 3D image analysis of root architecture and anatomy; and validated genes and genomic selection models to deploy traits for deeper rooting in maize breeding. Each DEEPER technology is transformative in its own right, and exceeds existing technologies. They are mutually synergistic, deployable for field-grown plants, and are ready for application. The phenotyping and modeling technologies are readily applicable to many crops, and genetic leads in maize may have utility in other grasses. Taken as a whole they represent a transformative platform to develop deeper-rooted crops, with greater drought tolerance, reduced fertilizer requirement, and greater carbon sequestration.

59 BASIC BIOLOGICAL SCIENCES↗

Self‐Assembly Methods Induce Different Individual‐Polymer‐Block Solvation Responses

An understanding of block-specific responses to stimuli in self-assembled copolymers is essential for the effective design of responsive materials. Here, materials formed from different post-reaction processing methods of the same ROMP block copolymer exhibit different block-specific solvent responses, as characterized in situ by fluorescence lifetime imaging microscopy (FLIM). FLIM data were acquired by tagging the polar or nonpolar block separately with a covalently incorporated viscosity-sensitive fluorescent molecular rotor to measure the changing tightness or looseness of assembly upon changes in solvent composition. Rapid precipitation from an insoluble solvent to form a film results in tighter assembly and less difference in tightness/looseness between the two blocks. Further, it interrupts individual block-solvent response behavior. Both results indicate an apparent disruption of the core–shell assembly. This model from FLIM is further supported by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) data from isolated solids, which show tighter long-range interactions and more long-range order in these kinetically trapped states. Here, the experiments develop FLIM as a method for pinpointing stimuli-responsive behaviors from different processing methods to individual blocks. Together these outcomes provide a future handle for tailoring solvent-triggered assembly/disassembly behavior.

López, Pía A. [University of California, Irvine, C↗

Primary radiation damage in bone evolves via collagen destruction by photoelectrons and secondary emission self-absorption

X-rays are invaluable for imaging and sterilization of bones, yet the resulting ionization and primary radiation damage mechanisms are poorly understood. Here we monitor in-situ collagen backbone degradation in dry bones using second-harmonic-generation and X-ray diffraction. Collagen breaks down by cascades of photon-electron excitations, enhanced by the presence of mineral nanoparticles. We observe protein disintegration with increasing exposure, detected as residual strain relaxation in pre-stressed apatite nanocrystals. Damage rapidly grows from the onset of irradiation, suggesting that there is no minimal ‘safe’ dose that bone collagen can sustain. Ionization of calcium and phosphorous in the nanocrystals yields fluorescence and high energy electrons giving rise to structural damage that spreads beyond regions directly illuminated by the incident radiation. Our findings highlight photoelectrons as major agents of damage to bone collagen with implications to all situations where bones are irradiated by hard X-rays and in particular for small-beam mineralized collagen fiber investigations.

36 MATERIALS SCIENCE↗

Sulphur variations in annually layered stalagmites using benchtop micro-XRF

Variation of sulphur in annually laminated stalagmites can be used to infer the impact of past volcanic activities, anthropogenic pollution, and climate change due to increased bushfire activity. The synchrotron radiation micro-X-Ray fluorescence (SR-XRF) microprobe is a powerful tool to analyse and image sulphur recorded in stalagmites with micrometre resolution. However, access to SR-XRF beamlines can be limited, so researchers must select the most promising stalagmites for imaging. Benchtop micro-XRF is an effective tool for trace elemental analysis of speleothem samples and is a candidate for routine laboratory measurement of sulphur along stalagmite laminae and screening for SR-XRF. Here, this study describes a protocol using matrix-matched standards to measure annual variations of sulphur at trace to percent level along the laminae of two Western Australian stalagmites, one of which already having been analysed using SR-XRF. Parameters that affected quantitation include X-ray tube voltage and current, spot size of the X-ray beam and stalagmite surface roughness and porosity. The use of a 20 μm X-ray spot size provides sub-annual spatial resolution that can be completed in an overnight scan. The features in a 1000 point micro-XRF analysis of sulphur along a 20 mm transect show good consistency with SR-XRF microprobe data. Micro-XRF mapping was also performed to produce chemical images on the stalagmite and compared with Raman and X-ray diffraction (XRD) to confirm that the stalagmite is exclusively calcite, with no aragonite, and that the source of sulphur in the samples was gypsum and anhydrite. Regions of very high sulphur in the micro-XRF maps were found to be artefacts due to diffraction of the incident beam but these could be efficiently removed by using a multiple point statistics approach to produce a clean image suitable for analysis of the laminae. This work shows the potential of micro-XRF for routine analysis of sulphur in stalagmites, and to streamline sample characterisation before SR-XRF imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resolution-enhanced X-ray fluorescence microscopy via deep residual networks

Abstract Multimodal hard X-ray scanning probe microscopy has been extensively used to study functional materials providing multiple contrast mechanisms. For instance, combining ptychography with X-ray fluorescence (XRF) microscopy reveals structural and chemical properties simultaneously. While ptychography can achieve diffraction-limited spatial resolution, the resolution of XRF is limited by the X-ray probe size. Here, we develop a machine learning (ML) model to overcome this problem by decoupling the impact of the X-ray probe from the XRF signal. The enhanced spatial resolution was observed for both simulated and experimental XRF data, showing superior performance over the state-of-the-art scanning XRF method with different nano-sized X-ray probes. Enhanced spatial resolutions were also observed for the accompanying XRF tomography reconstructions. Using this probe profile deconvolution with the proposed ML solution to enhance the spatial resolution of XRF microscopy will be broadly applicable across both functional materials and biological imaging with XRF and other related application areas.

36 MATERIALS SCIENCE↗

Spatiotemporal and Statistical Mapping of Transition Metal Equilibria in Alkaline Media

Transition metal dissolution and redeposition (D/R) kinetics in alkaline media play a critical role in various chemical and electrochemical processes. Competitive reaction kinetics between different transition metals can modulate individual metal behavior in these processes. To date, these phenomena have remained largely unmeasured, and even when captured, they are difficult to statistically characterize due to their dynamic nature, simultaneous occurrence, and spatially heterogeneous nature. Here, in this study, we develop a statistical analysis framework based on in situ and operando X-ray fluorescence microscopy (XFM) to investigate the relative D/R kinetics of multiple transition metals in alkaline media. By employing statistical analysis, we quantify the spatial distribution of D/R species and assess the rate at which the system reaches equilibrium under varying reaction conditions. We show that pH does not simply change the rate of dissolution and redeposition, but reorganizes the cross-element kinetic correlations among Ni, Fe, and Mn and accelerates the spatial equilibration of D/R events, as quantified through correlation analysis, reaction-rate estimation, probability function distributions, and texture-based monitoring statistics. Additionally, we demonstrate how modifying the solvent environment can influence D/R kinetics, providing a pathway for tuning materials synthesis and process optimization. Our study offers valuable insights into the complex interplay between different transition metals and provides a reliable statistical framework for spatial analysis of diverse imaging data sets, enabling deeper extraction of latent information across multiple modalities.

36 MATERIALS SCIENCE↗

Translocations are induced in hematopoietic stem cells after irradiation of fetal mice

Abstract Although mammalian fetuses have been suggested to be sensitive to radiation, an increased frequency of translocations was not observed in blood lymphocytes from atomic bomb (A-bomb) survivors who were exposed to the bomb in utero and examined as adults. Since experiments using hematopoietic cells of mice and rats confirmed this finding, it was hypothesized that either irradiated fetal hematopoietic stem cells (f-HSCs) cannot generate exchange-type chromosomal aberrations or cells bearing induced aberrations are eliminated before the animals reach adulthood. In the present study, pregnant mice (12.5–15.5 days post coitum [dpc]) were irradiated with 2 Gy of X-rays and long-term HSCs (LT-HSCs) were isolated 24 h later. Multicolor fluorescence in situ hybridization (mFISH) analysis of LT-HSC clones proliferated in vitro showed that nine out of 43 (21%) clones from fetuses and 21 out of 41 (51%) clones from mothers bore translocations. These results indicate that cells with translocations can arise in mouse f-HSCs but exist at a lower frequency than in the mothers 24 h after X-ray exposure. Thus, it seems likely that translocation-bearing f-HSCs are generated but subsequently disappear, so that the frequency of lymphocyte translocations may decrease and reach the control level by the time the animals reach adulthood.

60 APPLIED LIFE SCIENCES↗

3D printed water-stable Cd-doped Cs 4 MnBi 2 Cl 12 /polylactic acid perovskite/polymer composites for high-flux X-ray scintillation

Stable and efficient X-ray scintillators are crucial for medical diagnostics, industrial, and defense applications. However, conventional scintillator technologies face a trade-off between stability, optimal performance, and sustainability. Herein, we introduce 3D-printed Cs 4 MnBi 2 Cl 12 (Pero1) and Cs 4 Cd 0.68 Mn 0.32 Bi 2 Cl 12 (Pero2) perovskite microcrystals embedded within a polylactic acid (PLA) polymer composite as X-ray scintillators, combining efficiency, stability, and sustainability. The orange luminescent perovskite powder phosphors exhibited poor water stability, which was successfully addressed through incorporation into PLA via filament extrusion and fused deposition modeling (FDM) 3D printing. The resulting composite films demonstrated remarkable water stability while maintaining uniform orange emission throughout the polymer matrix, as confirmed by 3D topography scanning and X-ray fluorescence mapping. Structural characterization revealed minimal chemical interaction between the perovskite and PLA matrix, with the composites retaining their crystalline properties. The PLA-Pero2 composite exhibited superior optical properties, with a photoluminescence quantum yield of 47%, nearly 17 times higher than that of PLA-Pero1 (2.8%), attributed to the effective suppression of non-radiative decay pathways through Cd 2+ doping. Under hard X-ray irradiation at synchrotron beamlines, both composites exhibited excellent radioluminescence, with emission peaks at 605 nm, a linear response across a wide X-ray flux range, and remarkable radiation stability, showing less than 3% intensity degradation after 600 seconds of continuous high-dose exposure. The PLA-Pero2 composite achieved a spatial resolution of 5 line pairs per millimeter and a contrast ratio of 0.255. These performance metrics, combined with the polymer's biodegradability and scalability through additive manufacturing, position PLA-based composites as a more sustainable alternative to conventional petroleum-based polymer scintillators for next-generation medical imaging, radiation monitoring, and industrial radiography applications.

3D Printing↗

Benchmarking of X‐Ray Fluorescence Microscopy with Ion Beam Implanted Samples Showing Detection Sensitivity of Hundreds of Atoms

Abstract Single impurities in insulators are now often used for quantum sensors and single photon sources, while nanoscale semiconductor doping features are being constructed for electrical contacts in quantum technology devices, implying that new methods for sensitive, non‐destructive imaging of single‐ or few‐atom structures are needed. X‐ray fluorescence (XRF) can provide nanoscale imaging with chemical specificity, and features comprising as few as 100 000 atoms have been detected without any need for specialized or destructive sample preparation. Presently, the ultimate limits of sensitivity of XRF are unknown – here, gallium dopants in silicon are investigated using a high brilliance, synchrotron source collimated to a small spot. It is demonstrated that with a single‐pixel integration time of 1 s, the sensitivity is sufficient to identify a single isolated feature of only 3000 Ga impurities (a mass of just 350 zg). With increased integration (25 s), 650 impurities can be detected. The results are quantified using a calibration sample consisting of precisely controlled numbers of implanted atoms in nanometer‐sized structures. The results show that such features can now be mapped quantitatively when calibration samples are used, and suggest that, in the near future, planned upgrades to XRF facilities might achieve single‐atom sensitivity.

36 MATERIALS SCIENCE↗

X-ray fluorescence and XANES spectroscopy revealed diverse potassium chemistries and colocalization with phosphorus in the ectomycorrhizal fungus Paxillus ammoniavirescens

Ectomycorrhizal (ECM) fungi play a major role in forest ecosystems and managed tree plantations. Particularly, they facilitate mineral weathering and nutrient transfer towards colonized roots. Among nutrients provided by these fungi, potassium (K) has been understudied compared to phosphorus (P) or nitrogen (N). The ECM fungus Paxillus ammoniavirescens is a generalist species that interacts with the root of many trees and can directly transfer K to them, including loblolly pine. However, the forms of K that ECM fungi can store is still unknown. Here, we used synchrotron potassium X-ray fluorescence (XRF) and K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy on P. ammoniavirescens growing in axenic conditions to investigate the K chemistries accumulating in the center and the edge of the mycelium. We observed that various K forms accumulated in different part of the mycelium, including K-nitrate (KNO 3 ), K-C-O compounds (such as K-tartrate K 2 (C 4 H 4 O 6 ) and K-oxalate (K 2 C 2 O 4 )), K-S and K-P compounds. Saprotrophic fungi have been shown to excrete carboxylic acids, which in turn play a role in soil mineral weathering. Our finding of several K counter-ions to carboxylic acids may suggest that, besides their direct transfer to colonized roots, K ions can also be involved in the production of compounds necessary for sourcing nutrients from their surrounding environment by ECM fungi. Additionally, this work reveals that XANES spectroscopy can be used to identify the various forms of K accumulating in biological systems.

Ectomycorrhizal symbiosis↗

Dynamic zinc fluxes regulate meiotic progression in Caenorhabditis elegans

Abstract Zinc influx and efflux events are essential for meiotic progression in oocytes of several mammalian and amphibian species, but it is less clear whether this evolutionary conservation of zinc signals is also important in late-stage germline development in invertebrates. Using quantitative, single cell elemental mapping methods, we find that Caenorhabditis elegans oocytes undergo significant stage-dependent fluctuations in total zinc content, rising by over sevenfold from Prophase I through the beginning of mitotic divisions in the embryo. Live imaging of the rapid cell cycle progression in C. elegans enables us to follow changes in labile zinc pools across meiosis and mitosis in single embryo. We find a dynamic increase in labile zinc prior to fertilization that then decreases from Anaphase II through pronuclear fusion and relocalizes to the eggshell. Disruption of these zinc fluxes blocks extrusion of the second polar body, leading to a range of mitotic defects. We conclude that spatial temporal zinc fluxes are necessary for meiotic progression in C. elegans and are a conserved feature of germ cell development in a broad cross section of metazoa.

59 BASIC BIOLOGICAL SCIENCES↗

Association between soil organic carbon and calcium in acidic grassland soils from Point Reyes National Seashore, CA

All data is collected from across 3 soil cores spanning a pH gradient at Point Reyes National Seashore, as part of a recent publication. The bulk data csv includes hygroscopic moisture content, soil pH, total C and N values, particle size distributions, cation exchange capacity and extractable cations. The STXM data package includes raw spectra data from scanning transmission X-ray microscopy C near-edge X-ray absorption fine structure spectroscopy analysis, extracted from STXM Image Reader analysis and then subsequently normalised in Athena (see details in paper). The data file also contains a bulk chemistry and mineralogy dataset, including total and trace element contents from 3 depths and mineral compositions as measured at BL 11-3 SSRL and semi-quantified in HighScore. Finally the final data file is calcium K-edge X-ray absorption near-edge structure spectroscopy (BL 4-3) and micro-XANES and micro-X-ray fluorescence (BL 14-3b) data.

54 ENVIRONMENTAL SCIENCES↗

Rational design of a genetically encoded NMR zinc sensor

Elucidating the biochemical roles of the essential metal ion, Zn 2+ , motivates detection strategies that are sensitive, selective, quantitative, and minimally invasive in living systems. Fluorescent probes have identified Zn 2+ in cells but complementary approaches employing nuclear magnetic resonance (NMR) are lacking. Recent studies of maltose binding protein (MBP) using ultrasensitive 129 Xe NMR spectroscopy identified a switchable salt bridge which causes slow xenon exchange and elicits strong hyperpolarized 129 Xe chemical exchange saturation transfer (hyper-CEST) NMR contrast. To engineer the first genetically encoded, NMR-active sensor for Zn 2+ , we converted the MBP salt bridge into a Zn 2+ binding site, while preserving the specific xenon binding cavity. The zinc sensor (ZS) at only 1 μM achieved ‘turn-on’ detection of Zn 2+ with pronounced hyper-CEST contrast. This made it possible to determine different Zn 2+ levels in a biological fluid via hyper-CEST. ZS was responsive to low-micromolar Zn 2+ , only modestly responsive to Cu 2+ , and nonresponsive to other biologically important metal ions, according to hyper-CEST NMR spectroscopy and isothermal titration calorimetry (ITC). Protein X-ray crystallography confirmed the identity of the bound Zn 2+ ion using anomalous scattering: Zn 2+ was coordinated with two histidine side chains and three water molecules. Penta-coordinate Zn 2+ forms a hydrogen-bond-mediated gate that controls the Xe exchange rate. Metal ion binding affinity, 129 Xe NMR chemical shift, and exchange rate are tunable parameters via protein engineering, which highlights the potential to develop proteins as selective metal ion sensors for NMR spectroscopy and imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scanning structural mapping at the Life Science X-ray Scattering Beamline

This work describes the instrumentation and software for microbeam scattering and structural mapping at the Life Science X-ray Scattering (LiX) beamline at NSLS-II. Using a two-stage focusing scheme, an adjustable beam size between a few micrometres and a fraction of a millimetre is produced at the sample position. Scattering data at small and wide angles are collected simultaneously on multiple Pilatus detectors. A recent addition of an in-vacuum Pilatus 900k detector, with the detector modules arranged in a C-shaped configuration, has improved the azimuthal angle coverage in the wide-angle data. As an option, fluorescence data can be collected simultaneously. Fly scans have been implemented to minimize the time interval between scattering patterns and to avoid unnecessary radiation damage to the sample. For weakly scattering samples, an in-vacuum sample environment has been developed here to minimize background scattering. Data processing for these measurements is highly sample-specific. To establish a generalized data process workflow, first the data are reduced to reciprocal coordinates at the time of data collection. The users can then quantify features of their choosing from these intermediate data and construct structural maps. As examples, results from in-vacuum mapping of onion epidermal cell walls and 2D tomographic sectioning of an intact poplar stem are presented.

36 MATERIALS SCIENCE↗

Measuring X-Ray Emission Line Shapes in Neutral Species for XRISM Calibration

Space X-ray spectrometers such as the Resolve instrument on XRISM require precise calibration in order to interpret the spectra of astrophysical objects. Key components of the calibration are the energy scale and the core line spread function, both of which vary with photon energy. A major issue in the calibration of high-resolution spectrometers is locating good calibrators with well-known and stable intrinsic line shapes. Neutral fluorescence is widely used, but inner-shell transitions in neutral atoms often exhibit complex, poorly documented line shapes that vary with excitation conditions. Here, in this study, we present empirical measurements of K-shell transitions in neutral O and F below 1 keV using an engineering model XRISM calorimeter array, an electron bombardment modulated X-ray source, and an electron beam ion trap (EBIT) to provide a precise energy reference. In addition, we report measurements of the Mo Lα complex with the transition-edge microcalorimeter spectrometer (TEMS), which reveal strong satellite structure and sensitivity of the line shape to the incident exciting spectrum. Together, these results demonstrate the need for empirical line-shape models, highlight the nonstationary nature of neutral fluorescence features, and define a path toward developing transfer standards for XRISM and future precision instruments such as Athena/X-IFU.

Astronomy and AstroPhysics↗

Multimodal correlative imaging and modelling of phosphorus uptake from soil by hyphae of mycorrhizal fungi

Phosphorus (P) is essential for plant growth. Arbuscular mycorrhizal fungi (AMF) aid its uptake by acquiring P from sources distant from roots in return for carbon. Little is known about how AMF colonise soil pore-space, and models of AMF-enhanced P-uptake are poorly validated. We used synchrotron X-ray computed tomography to visualize mycorrhizas in soil and synchrotron X-ray fluorescence/X-ray absorption near edge structure (XRF/XANES) elemental mapping for P, sulphur (S) and aluminium (Al) in combination with modelling. We found that AMF inoculation had a suppressive effect on colonisation by other soil fungi and identified differences in structure and growth rate between hyphae of AMF and nonmycorrhizal fungi. Our results showed that AMF co-locate with areas of high P and low Al, and preferentially associate with organic-type P species over Al-rich inorganic P. We discovered that AMF avoid Al-rich areas as a source of P. Sulphur-rich regions were found to be correlated with higher hyphal density and an increased organic-associated P-pool, whilst oxidized S-species were found close to AMF hyphae. Increased S oxidation close to AMF suggested the observed changes were microbiome-related. Our experimentally-validated model led to an estimate of P-uptake by AMF hyphae that is an order of magnitude lower than rates previously estimated – a result with significant implications for the modelling of plant–soil–AMF interactions.

79 ASTRONOMY AND ASTROPHYSICS↗

Tonian Carbonates Record Phosphate-Rich Shallow Seas

The early-middle Neoproterozoic is thought to have witnessed significant perturbations to marine P cycling, in turn facilitating the rise of eukaryote-dominated primary production. However, with few robust constraints on aqueous P concentrations, current understanding of Neoproterozoic P cycling is generally model-dependent. To provide new geochemical constraints, we combined microanalytical data sets with solid-state Nuclear Magnetic Resonance, synchrotron-based X-ray Absorption Near Edge Structure spectroscopy, and micro-X-ray Fluorescence imaging to characterize the speciation and distribution of P in Tonian shallow-water carbonate rocks. These data reflect shallow water phosphate concentrations 10–100× higher than modern systems, supporting the hypothesis that tectonically-driven influxes in P periodically initiated kinetically-controlled CaCO 3 deposition, in turn destabilizing marine carbonate chemistry, climate, and nutrient inventories. Alongside these observations, a new compilation and statistical analysis of mudstone geochemistry data indicates that, in parallel, C org and P burial increased across later Tonian continental margins until becoming decoupled at the close of the Tonian, implicating widespread N-limitation triggered by increasing atmospheric O 2 .

58 GEOSCIENCES↗