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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,333 records · Page 74
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Optimizing a Knowledge-driven Prospectivity Model for Gold Deposits Within Peräpohja Belt, Northern Finland

This paper combines knowledge- and data-driven prospectivity mapping approaches by using the receiver operating characteristics (ROC) spatial statistical technique to optimize the process of rescaling input datasets and the process of data integration when using a fuzzy logic prospectivity mapping method. The methodology is tested in an active mineral exploration terrain within the Paleoproterozoic Peräpohja Belt (PB) in the Northern Fennoscandian Shield, Finland. The PB comprises a greenschist to amphibolite facies, complexly deformed supracrustal sequence of variable quartzites, mafic volcanic rocks and volcaniclastic rocks, carbonate rocks, black shales, mica schists and graywackes. These formations were deposited on Archean basement and 2.44 Ga layered intrusions, during the multiple rifting of the Archean basement (2.44–1.92 Ga). Younger intrusive units in the PB comprise 2.20–2.13 Ga gabbroic sills or dikes and 1.98 Ga A-type granites. Metamorphism and complex deformation of the PB took place during the Svecofennian orogeny (1.9–1.8 Ga) and were followed by intrusions of post-orogenic granitoids (1.81–1.77 Ga). The recent mineral exploration activities have indicated several gold-bearing mineral occurrences within the PB. The Rompas Au-U mineralization is hosted within deformed and metamorphosed calc-silicate veins enclosed within mafic volcanic rocks and contains uranium-bearing zones without gold and very high-grade (>10,000 g/t Au) gold pockets with uraninite and uraninite-pyrobitumen nodules. In the vicinity of the Rompas, a magnesium skarn hosted disseminated-stockwork gold mineralization was also recognized at the Palokas-Rajapalot prospect. The exploration criteria translated into a fuzzy logic prospectivity model included data derived from regional till geochemistry (Fe, Cu, Co, Ni, Au, Te, K), high-resolution airborne geophysics (magnetic field total intensity, electromagnetic, gamma radiation), ground gravity and regional bedrock map (structures). The current exploration licenses and exploration drilling sites for gold were used to validate the knowledge-driven mineral prospectivity model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

A Feature-Based Stochastic Permeability of Shale: Part 2–Predicting Field-Scale Permeability

We report that in a recent numerical study, it was demonstrated that characterizing reservoir permeability in terms of rock’s quality, as observed in lab and field, is the most important step before implementing an enhanced oil recovery operation or drilling a new well in a tight formation. In that study, it was shown that permeable features in shale-like organic matter (OM) and fractures were the only regions that allowed some reasonable movement of fluid, whereas inorganic matter (iOM) that occupies larger pore volume with significant saturation of hydrocarbons has extremely low permeability that did not allow any reasonable fluid movement to affect production. That study demonstrated the importance of characterizing reservoir heterogeneity in shale in order to economically exploit the shale resource. This study proposes a method to predict spatially heterogeneous field-scale permeability of shale in terms of natural fractures, and matrix (iOM and OM). The method developed in Part 1 is combined with a history-matching process that uses only readily available information from lab-scale and outcrop (information from geologists) to predict field-scale permeability. The method also ensures consistency between the underlying fracture distribution and optimally matched fracture lengths and their apertures, in addition to accounting for random distribution of fractures and their abundance. Optimized parameters of fracture distribution are used to generate multiple realizations of geological model, and the “best-fitting” (most-likely) permeability scenario is chosen by generating production response of each realization of the geological model and comparing them against the observed field production history. Finally, the novelty of the proposed to predict field-scale permeability is that it uses only readily available information while also ensuring consistency between the underlying fracture distribution and optimally matched fracture lengths and their apertures, in addition to accounting for random distribution of fractures and their abundance.

58 GEOSCIENCES↗
DOE OSTI2022

Interlaboratory Reproducibility of Contour Method Data in a High Strength Aluminum Alloy

The contour method for residual stress measurement has seen significant development, but an experimental reproducibility study utilizing physical samples has not been published. A double-blind reproducibly study is reported, having scope beginning with EDM cutting and ending with residual stress calculation. A reinforced I-beam sample geometry is identified for its unique residual stress profile when extracted from residual stress bearing quenched aluminum bar (7050-T74). Contour measurements are prescribed on a midplane of symmetry with dimensions 24.0 mm by 50.0 mm. Fourteen identically prepared samples are fabricated from a single long bar with well characterized and uniform residual stress. Five samples throughout the bar are identified for planning measurements to validate sample uniformity and overall suitability of the residual stress field. The planning measurements employ a range of techniques: contour method, neutron diffraction, and hole-drilling. Eight samples are distributed to an international group of participants to execute their standard measurement practice. A double-blind process is followed to provide anonymity. Results are provided by eight participants: six being self-similar and two being quite different, the latter set aside as outliers. An average residual stress field is established from non-outlying results and the spatial distribution of reproducibility standard deviation is determined. The average stress field ranges from -60 to 70 MPa and the reproducibility standard deviation averages 8.1 MPa on the measurement plane. The average reproducibility standard deviation is about 3 × larger for points within 1.0 mm of plane boundaries (17.6 MPa) than for the remaining points (6.1 MPa). Reproducibility standard deviation (among different labs) for contour method residual stress measurement is found to be very similar to repeatability standard deviation (in a single lab) reported in prior work. The reproducibility observed here, for the entire measurement process, is also similar to that found in a prior reproducibility study limited to contour method data analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Physics-Informed and Data-Driven Prediction of Residual Stress in Three-Dimensional Machining

Efficient and reliable prediction of machining-induced residual stress (RS) is a key requirement for truly integrated computational materials engineering (ICME). Currently available process modeling approaches, including empirical, analytical, and numerical methodologies lack predictive power and require substantial calibration and validation data. Moreover, most model-based approaches consider only two-dimensional (2D) (i.e., orthogonal), cutting processes. Meanwhile, industrial processes such as milling, turning, and drilling are inherently three-dimensional (3D). The present work attempts to bridge the gap between 2D and 3D through careful consideration of the process physics, including geometric, kinematic, and size-effect constraints to realize robust prediction of how RS develops in 3D machining. Using a novel in-situ experimental technique and digital image correlation (DIC) to determine equivalent Hertzian contact widths, contact pressures, and friction coefficients, the proposed methodology leverages a discretized conversion algorithm that includes multi-pass shakedown effects. This paper presents a semi-analytical model to predict machining-induced RS in 3D turning operations, which are used representatively for 3D processes more generally. Rather than follow a ‘brute force’ 3D FEM approach or conduct countless experiments to train a purely data-driven machine learning algorithm, the proposed approach builds on previous 2D modeling work. Through careful consideration of the process physics, including complex geometry/kinematic considerations of 3D turning, the authors demonstrated an experimentally calibrated approach, as well as validation based on published RS data. Model predictions and previously published measurement data of RS depth profiles for turning of Inconel 718 were compared for a range of process parameters. Correlation between the proposed 3D model and validation data was found to be within the margin of experimental error for most conditions. The proposed model appears to capture the overall behavior of 3D RS depth profiles with acceptable accuracy, particularly the key metrics of near-surface stress, peak stress magnitude and location, as well as overall stress profile depth. This report presents a physics-informed, data-driven approach for efficient calibration of a 2D model for machining-induced RS through DIC analysis of in-situ characterized subsurface displacement fields.

42 ENGINEERING↗
DOE OSTI2018

Effect of Weld Consumable Conditioning on the Diffusible Hydrogen and Subsequent Residual Stress and Flexural Strength of Multipass Welded P91 Steels

P91 steel weld joint was prepared using the shielded metal arc welding process and four different conditions of weld consumable that provide the different levels of diffusible hydrogen in deposited metal. In the present research, the effects of diffusible hydrogen content on the flexural strength, lower critical stress, and tensile strength of P91 steel welds were also determined with respect to different electrode conditions. To investigate the effect of diffusible hydrogen on multipass welding, top and root side flexural tests were performed. The residual stresses (axial stress and transverse stress) were also measured using the blind hole drilling method for different conditions of welding consumable. The peak value of residual stresses was measured at the center of the weld fusion zone. The maximum value of transverse stress was measured to be 355 MPa for case II (6.21 mL/100 g of diffusible hydrogen), while the maximum axial stress was about 218 MPa for case IV (12.43 mL/100 g of diffusible hydrogen). A three-dimensional finite element simulation was also performed to predict the residual stress distribution and thermal profile along the welded joint. The experimentally determined residual stresses correlated well with the numerically estimated residual stresses. The diffusible hydrogen content was not observed to have any significant effect on the residual stresses. The corrected residual stress values were also predicted by considering the plasticity-induced error. However, the flexural performance of the welded joint was affected by the diffusible hydrogen content. The top and root flexural strength was measured to be optimum for the low level of diffusible hydrogen content, and the values decreased with an increase in diffusible hydrogen content.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Residual Stresses in Explosively Welded Plates Made of Titanium Grade 12 and Steel with Interlayer

Distributions of residual stress components in explosively welded three-layer plate composed of titanium Grade 12, titanium Grade 1 and SA516 Grade 70 steel are investigated in this paper. The study applied the sectioning and the hole-drilling strain gage methods for residual stress measurement. The results have shown an inhomogeneous residual stress distribution, approximated by fourth-order polynomial along the thickness of a three-layer plate. Biaxial compressive residual stress state is observed in titanium Grade 12 and Grade 1 layers which change to tensile type in the vicinity of the interface between titanium Grade 1 and steel. Microstructure observation reveals the presence of the adiabatic shear bands in titanium Grade 12 layer at the interface with titanium Grade 1 interlayer. The observed distribution of residual stress components is justified by the occurrence of the shock wave phenomena.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Microstructure and Friction-Wear Behavior of Multi-arc Ion Plating TiAlNC Ceramic Coating on WC-6%Co Substrate

Nanocomposite coating could be used for machining tools, which can be used for cutting, drilling, milling, whetting, profiling, honing and superfinishing of various materials with high productivity. In this work, the TiAlNC ceramic coating was prepared by multi-arc ion plating method on WC-6%Co substrate. The microstructure and morphology of the coating were observed by scanning electron microscopy and transmission electron microscopy. The phase and chemical composition of the coating were determined by x-ray diffraction and x-ray energy-dispersive spectroscopy, respectively. The adhesive force of the coating was measured by a scratch tester, at the same time the friction-wear behavior of the coating was studied. The results show that there were TiN and (Ti,Al)(N,C) two phases, and there was the coexistence of amorphous and nanocrystalline in the coating. The chemical composition of the coating was composed of 20 ± 9 at.% Ti, 16 ± 5 at.% Al, 39 ± 5 at.% N and 25 ± 10 at.% C. The thickness of the coating was about 4.5 μm. The average root mean square value of the surface roughness was 225 ± 16 nm. A critical force for coating failure in scratch testing was about 25 N. The friction coefficients of the substrate and the coating were 0.55 and 0.35, respectively. The ceramic coating could improve the wear resistance of the substrate.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Impact of elliptical boreholes on in situ stress estimation from leak-off test data

We developed an inversion technique to determine in situ stresses for elliptical boreholes of arbitrary trajectory. In this approach, borehole geometry, drilling-induced fracture information, and other available leak-off test data were used to construct a mathematical model, which was in turn applied to finding the inverse of an overdetermined system of equations. The method has been demonstrated by a case study in the Appalachian Basin, USA. The calculated horizontal stresses are in reasonable agreement with the reported regional stress study of the area, although there are no field measurement data of the studied well for direct calibration. The results also indicate that 2% of axis difference in the elliptical borehole geometry can cause a 5% difference in minimum horizontal stress calculation and a 10% difference in maximum horizontal stress calculation.

42 ENGINEERING↗
DOE OSTI2017

Spontaneous imbibition of water and determination of effective contact angles in the Eagle Ford Shale Formation using neutron imaging

Understanding of fundamental processes and prediction of optimal parameters during the horizontal drilling and hydraulic fracturing process results in economically effective improvement of oil and natural gas extraction. Although, the modern analytical and computational models can capture fracture growth, there is a lack of experimental data on spontaneous imbibition and wettability in oil and gas reservoirs for the validation of further model development. In this work, we used neutron imaging to measure the spontaneous imbibition of water into fractures of Eagle Ford Shale with known geometries and fracture orientations. An analytical solution for a set of nonlinear second-order differential equations was applied to the measured imbibition data to determine effective contact angles. The analytical solution fit the measured imbibition data reasonably well and determined effective contact angles were slightly higher than static contact angles due to effects of in-situ changes in velocity, surface roughness, and heterogeneity of mineral surfaces on the fracture surface. Additionally, small fracture widths may have retarded imbibition and affected model fits, which suggests that average fracture widths are not satisfactory for modeling imbibition in natural systems.

DiStefano, Victoria H. (ORCID:0000000160239716)↗
DOE OSTI2022

Integration of Large-Scale Electrical Imaging into Geological Framework Development and Refinement

Geologic framework models (GFMs) are critical to the construction of reliable simulation models of groundwater flow and contaminant transport. To support GFM development, direct information (e.g., core samples, fluid samples, hydraulic testing) tends to be sparse and separated by large distances relative to the spatial scales of aquifer heterogeneity. There are additional challenges associated with highly contaminated legacy waste sites, where drilling is particularly costly, and invasive sampling requires specialized handling and disposal of hazardous materials. At these sites in particular, non-invasive geophysical imaging can play an important role in filling spatial gaps between boreholes and reducing characterization costs by optimizing and minimizing the number of necessary boreholes. Here this paper presents a case study demonstrating the use of large-scale (> 30 km 2 ) electrical mapping to identify hydrostratigraphy and potential paleochannels at the Hanford Site, located in Washington State, USA. In two field campaigns, over 36 line-kilometers of electrical resistivity tomography (ERT) data were collected along 14 transects. ERT surveys were sited and performed to image critical aspects (e.g., paleochannels, stratigraphic contacts) of the subsurface, demonstrating a general workflow for integrating ERT with GFM development. Inconsistencies between the GFM and ERT were catalogued to provide a basis for future site characterization using complementary geophysical methods and (or) direct sampling.

58 GEOSCIENCES↗
DOE OSTI2019

Directional and oscillating residual stress on the mesoscale in additively manufactured Ti-6Al-4V Mesoscale and anisotropic residual stress in additive manufacturing of Ti-6Al-4V

In additive manufacturing of metals as compared to conventional processing, the directional track-by-track and layer-by-layer nature of the fabrication process can lead to residual stresses that locally are both directionally and spatially heterogeneous. Much of the existing literature has focused either on the macroscale residual stress inside the entire part, or on the microscale residual stresses that are created around a scan vector, thereby neglecting the intermediate length-scale of the different layers. The objective of this research is to investigate such mesoscale residual stress distributions across several layers in Ti-6Al-4V components produced by laser metal deposition process. The incremental centre hole drilling and incremental slitting methods provide measurements with excellent spatial resolution within and across the layer length scale. Here in this work, the two methods complemented each other to quantify both mesoscale and directional variations of residual stress that correlate with the deposition pattern. Lastly, our findings also provide strong evidence that an oscillatory residual stress variation persists even after thermal cycling that occurs during deposition of subsequent layers.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Elucidating the effect of preheating temperature on melt pool morphology variation in Inconel 718 laser powder bed fusion via simulation and experiment

In laser powder bed fusion (L-PBF) additive manufacturing, the mechanical performance, microstructure and defects of fabricated parts are closely associated with the melt pool morphology, e.g., its dimension and shape through the building process. Past studies have largely focused on how the process parameters such as laser power and scan speed affect melt pool characteristics. In this study, the melt pool morphology variation as a function of preheating temperature in the conduction, transition, and keyhole regimes and the underlying mechanisms in each regime are investigated through ex-situ sample characterization and computation thermal fluid dynamics (CtFD) simulation. Single tracks with different combinations of laser power and scan speed are deposited on an Inconel 718 bare plate preheated to a temperature range of 100–500 °C in the experiment. Significant changes are observed in melt pool morphology as a function of preheating temperature from optical measurements of melt track cross sections. The depth of melt pool in the three regimes increases monotonically with preheating temperature, e.g., at 500 °C, the experimental melt pool depth is increased by 49% in conduction regime, 34% in transition regime and 33% in keyhole regime, respectively, while the variation of melt pool width in each regime does not all follow an increasing trend but depends on the melt pool regimes. Melt pool width variation in the conduction and transition regimes is found to depend on the enhanced heat conduction directly related to temperature dependent thermal properties. Through validated CtFD simulations, it is found that in the keyhole regime the evaporation mass, recoil pressure, and laser drilling effect is enhanced with higher preheating temperature, which gives rise to a deeper melt pool. The simulations also reveal that preheating temperature significantly elongates the melt track length due to the increased flow rate and strong recoil pressure that accelerates the backward flow.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Solar-driven efficient methane catalytic oxidation over epitaxial ZnO/La 0.8 Sr 0.2 CoO 3 heterojunctions

Gas flaring in oil/gas drilling and gas leakage in natural gas power plant lead to significant energy loss and environmental burden. Here, solar-driven efficient methane oxidation was demonstrated under high velocity continuous flow over the ZnO/La 0.8 Sr 0.2 CoO 3 (ZnO/LSCO) heterojunctions. The ZnO/LSCO heterojunctions enable a unique epitaxial hetero-interface, which effectively regulates the electron transfer between Zn 3d -O 2p hybrid orbital in ZnO and Co e g orbital in LSCO and promotes the rapid generation and refill of oxygen vacancy with unpaired electron (V o ), thus enhancing the activity and mobility of surface lattice oxygen in ZnO/LSCO. Under solar illumination, the synergy of photothermal and photocatalytic effect boosts the reversible electron transfer in the interface, which further activates surface lattice oxygen, resulting in a ~2 times higher methane oxidation activity. Such a solar-driven system not only enables a promising pathway for emitted methane utilization, but also provides an advanced catalyst design concept of epitaxial interface construction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The value of in-reservoir energy storage for flexible dispatch of geothermal power

Geothermal systems making use of advanced drilling and well stimulation techniques have the potential to provide tens to hundreds of gigawatts of clean electricity generation in the United States by 2050. With near-zero variable costs, geothermal plants have traditionally been envisioned as providing “baseload” power, generating at their maximum rated output at all times. However, as variable renewable energy sources (VREs) see greater deployment in energy markets, baseload power is becoming increasingly less competitive relative to flexible, dispatchable generation and energy storage. Herein we conduct an analysis of the potential for future geothermal plants to provide both of these services, taking advantage of the natural properties of confined, engineered geothermal reservoirs to store energy in the form of accumulated, pressurized geofluid and provide flexible load-following generation. We develop a linear optimization model based on multi-physics reservoir simulations that captures the transient pressure and flow behaviors within a confined, engineered geothermal reservoir. We then optimize the investment decisions and hourly operations of a power plant exploiting such a reservoir against a set of historical and modeled future electricity price series. Further, we find that operational flexibility and in-reservoir energy storage can significantly enhance the value of geothermal plants in markets with high VRE penetration, with energy value improvements of up to 60% relative to conventional baseload plants operating under identical conditions. Across a range of realistic subsurface and operational conditions, our modeling demonstrates that confined, engineered geothermal reservoirs can provide large and effectively free energy storage capacity, with round-trip storage efficiencies comparable to those of leading grid-scale energy storage technologies. Optimized operational strategies indicate that flexible geothermal plants can provide both short- and long-duration energy storage, prioritizing output during periods of high electricity prices. Sensitivity analysis assesses the variation in outcomes across a range of subsurface conditions and cost scenarios.

15 GEOTHERMAL ENERGY↗
DOE OSTI2014

Geochemical and Mineralogical Investigation of Uranium in Multi–element Contaminated, Organic–rich Subsurface Sediment

Alluvial sediments characterized by an abundance of refractory or lignitic organic carbon compounds and reduced Fe and S bearing mineral phases have been identified through drilling activities at the U.S. Department of Energy’s (DOE) Integrated Field Research Challenge (IFRC) site at Rifle, CO. Regions of the subsurface from which such sediments are derived are referred to as Naturally Reduced Zones (NRZ). We conducted a study with NRZ sediments with the objective to: i.) Characterize solid phase contamination of U and other co-contaminants; ii.) Document the occurrence of potential U host minerals; iii.) Determine U valence state and micron scale spatial association with co-contaminants. Macroscopic (wet chemical batch extractions and a column experiment), microscopic (SEM-EDS), and spectroscopic (Mössbauer, µ-XRF and XANES) techniques were employed. Results showed that sediments’ solid phase had significant concentrations of U, S, As, Zn, V, Cr, Cu and Se, and a remarkable assortment of potential U hosts (sorbents and/or electron donors), such as Fe oxides (hematite, magnetite, Al-substituted goethite), siderite, reduced Fe(II) bearing clays, sulfides of different types, Zn sulfide framboids and multi – element sulfides. Multi-contaminants, micron size (ca. 5 to 30 µm) areas of mainly U(IV) and some U(VI), and/or other electron scavengers or donors such as Se, As, Cr, and V were discovered in the sediments, suggesting complex micron-scale system responses to transient redox conditions, and different extent and rates of competing U redox reactions than those of single contaminant systems. Collectively, the results improve our understanding and ability to predict U and NRZ’s complex behavior and will delineate future research directions to further study both the natural attenuation and persistence of contaminant plumes and their contribution to groundwater contamination.

bioavailability↗
DOE OSTI2017

Concrete alteration due to 55 years of exposure to river water: Chemical and mineralogical characterisation

This article presents a study on concrete alteration mechanisms due to 55 years of exposure to river water. Many hydro power structures in cold regions suffer from concrete deterioration at the waterline. Progressive disintegration of the concrete surface leads to exposure of the coarse aggregate and eventually the reinforcing steel. Concrete cylinders drilled out at four vertically different locations on the upstream face of a concrete dam were analysed by electron microprobe analysis, X-ray diffraction, thermogravimetry and scanning electron microscopy. Long-term exposure to the river water, which is regarded as soft water, has led to chemical and mineralogical zonation of the cement paste. Up to five zones with different chemical and mineralogical composition, parallel to the upstream face, were observed in the outermost 8–9 mm of the concrete. Decalcification, precipitation of secondary ettringite and the formation of a magnesium-rich silica gel constitute the major changes that define the zones.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A record of uranium-series transport at Nopal I, Sierra Pena Blanca, Mexico: Implications for natural uranium deposits and radioactive waste repositories

Studies of uranium-series (U-series) disequilibria within and around ore deposits provide valuable information on the extent and timing of actinide mobility, via mineral-fluid interaction, over a range of spatial and temporal scales. Such information is useful in studies of analogs of high-level nuclear-waste repositories, as well as for mining and mineral extraction sites, locations of previous nuclear weapons testing, and legacy nuclear waste contamination. In this study we present isotope dilution mass spectrometry U-series measurements for fracture-fill materials (hematite, goethite, kaolinite, calcite, dolomite and quartz) from one such analog; the Nopal I uranium ore deposit situated at Peña Blanca in the Chihuahua region of northern Mexico. The ore deposit is located in fractured, unsaturated volcanic tuff and fracture-fill materials from surface fractures as well as fractures in a vertical drill core have been analyzed. High uranium concentrations in the fracture-fill materials (between 12 and 7700 ppm) indicate uranium mobility and transport from the deposit. Furthermore, uranium concentrations generally decrease with horizontal distance away from the deposit but in this deposit there is no trend with depth below the surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Molybdenum isotope fractionation and speciation in a euxinic lake—Testing ways to discern isotope fractionation processes in a sulfidic setting

The molybdenum (Mo) isotope composition in euxinic shales has been used as a proxy for the global distribution of anoxic conditions in ancient oceans, and since more recently also as a proxy for sulfide concentrations in depositional environments. However, there is currently no way to distinguish isotope fractionation at low bottom water sulfide concentrations in ‘local’ basins from ‘global’ secular isotope variations associated with changing seawater composition. This uncertainty is challenging the use of Mo isotopes for paleoceanographic reconstructions. To explore this further, we present new data from sediments deposited over the past ~ 9800 years in one of the best studied euxinic localities in the world: Lake Cadagno in Switzerland. The sample set allows us to test ways to discern isotope fractionation processes at play in a highly restricted euxinic basin. Most of our drill core samples (n = 18) show high δ98Mo values similar to previously studied shallow sediments, indicative of quantitative Mo removal from the water column (Dahl et al. 2010a). However, a few samples (n = 3) deposited between about 1200 and 3400 years ago carry low δ98Mo values and have been isotopically fractionated in the lake. Sedimentological and geochemical characterizations show that these δ98Mo-fractionated sediments formed during times of frequent injection of O2- and sediment-rich river water into the deep sulfidic water column. A positive correlation between δ98Mo and sedimentary Mo contents suggests that isotope fractionation occurred during times of non-quantitative Mo removal, although Mn-oxide cycling at the chemocline might also contribute a subordinate proportion of (98Mo-depleted) molybdenum into the sulfidic zone. Sedimentary Mo/U enrichments relative to oxic lake water further supports the hypothesis that a particulate Mo shuttle was most efficient during times of quantitative Mo removal. Therefore, periods with inefficient Mo capture are ascribed to incomplete conversion of molybdate to particle reactive Mo species when bottom water H2S levels were low or less stable than today. Using XAFS spectroscopy, we found that the two distinct Mo compounds predominating in the sediments (MoIV-S and MoVI-OS) are not diagnostic for isotope fractionation that has occurred in Lake Cadagno. Instead, we infer that δ98Mo-fractionated products (forming via a low-sulfide Mo pathway) can be subsequently altered with little or no isotopic imprint during remobilization and re-precipitation (e.g., at higher sulfide levels in the sediments) as well as during post-depositional oxidation. Future work could investigate local δ98Mo-fractionation processes expressed in other euxinic settings and explore other sedimentary metrics to constrain the steps involved in the euxinic burial pathway(s). One tantalizing prospect of this is to distinguish between local bottomwater sulfide levels and variations in the fraction of global seafloor anoxia from the Mo isotope composition in ancient euxinic mudrocks.

58 GEOSCIENCES↗