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At least 541 records · Page 30

Algae/Wood Blends Hydrothermal Liquefaction and Upgrading: 2019 State of Technology

The fiscal year (FY) 2019 State of Technology (SOT) Assessment for a microalgae and woody biomass blend feedstock hydrothermal liquefaction (HTL) and biocrude upgrading system has been completed and reported here. This study is a preliminary economic analysis for this system. Inputs from the 2019 NREL open pond algae cultivation model provided microalgae seasonal flowrates and dewatered algae feedstock price. These inputs have been coupled with modeled experimental data from PNNL for algae/wood blends processed via HTL to assess the cost impacts. The TEA results demonstrated a 28% reduction in the conversion cost only from $1.22/gge in 2018 to $0.88/gge in 2019.

09 BIOMASS FUELS↗

An Eco-Friendly System for the Production of Value-Added Materials from Dairy Manure

A technoeconomic model has been developed to explore the viability of a two-stage anaerobic digester (AD) coupled with additional processes to increase the economic attractiveness of a new manure treatment system. The addition of a polyhydroxyalkanoate (PHA) reactor, algae cultivation system (ACS), and a biomass treatment system, such as, fast-pyrolysis or hydrothermal liquefaction (HTL) would further sequester carbon and nutrients, as well as add valuable products that can be sold or used on-site to mitigate costs. The Decision-support for Digester-Algae IntegRation for Improved Environmental and Economic Sustainability (DAIRIEES) model is used to evaluate the effectiveness and viability of this system to achieve economic and environmental sustainability by the dairy industry. The DAIRIEES model was used to evaluate the effectiveness and viability of this system to achieve economic viability and environmental sustainability by the dairy industry. A base case with mass flows and economics for a 10,000 herd dairy is considered. The integrated manure treatment system can reduce the amount of nitrogen released from the manure by 61.7%. If the ACS is not incorporated into the system, the nitrogen reduction drops to 19%. Similarly, the amount of phosphorus available for release to the environment is reduced by 37.4% with the full system, and by 26% for the system without the ACS. The results of the economic analysis indicate a net loss for the integrated system with algae cultivation. Without algae cultivation, the manure treatment system is profitable with a payback period of less than five years.

09 BIOMASS FUELS↗

Inorganic Ba-Sn Nanocomposite Materials for Sulfate Sequestration from Complex Aqueous Solutions

Selective sequestration of sulfate (SO42-) in the form of barite (BaSO4) from alkaline solutions of high ionic strength containing carbonate at high concentrations resembling legacy radioactive waste generated during plutonium cold war era production is problematic due to the preferential formation of BaCO3. Incorporation of sulfate into the insoluble and thermally stable BaSO4 phase can potentially benefit radioactive waste processing in reducing operational challenges and suppressing volatilization of other waste components such as technetium-99. To enhance selectivity of SO42- sequestration, a series of Ba(II)-Sn(IV) materials was prepared using simple hydrothermal synthesis from different Sn(II) and Sn(IV) precursors. Structural characterization indicated that all obtained products predominantly contained BaSn(OH)6 and Ba2SnO2(OH)4(H2O)10 crystalline phases which were disrupted upon exposure to SO42- due to formation of BaSO4. Performance of the Ba(II)-Sn(IV) materials was tested using complex alkaline solutions simulating radioactive waste containing 0.094 M SO42- and 0.5 M CO32- among other constituents. About 54 – 66% of SO42- was converted to BaSO4 when a quantity of Ba(II)-Sn(IV) material containing approximately a stoichiometric amount of Ba2+ relative to SO42- was used. In comparison, previous studies indicate negligible BaSO4 formation under similar conditions when a simple Ba2+ salt is used. This improvement is attributed to the selective replacement of the Ba(II) stannate by SO42-. Thermal stability of the sulfate-loaded product material up to 1100 °C was demonstrated. Obtained materials offer a convenient and economical option for the selective sequestration or removal of SO42- from carbonate containing solutions.

Johnson, Isaac↗

The Topography and Basin Deposits of the Equatorial Highlands: A MGS-Viking Synergistic Study

One of the greatest unresolved issues concerns the evolution of Mars early in its history; during the time period that accretion was winding down but the frequency of impacting debris was still heavy. Ancient cratered terrain that has only been moderately modified since the period of heavy bombardment covers about a quarter of the planet's surface but the environment during its formation is still uncertain. This terrain was dominantly formed by cratering. But unlike on the airless Moon, the impacting craters were strongly modified by other contemporary surface processes that have produced distinctive features such as: 1) dendritic channel networks, 2) rimless, flatfloored craters, 3) obliteration of most craters smaller than a few kilometers in diameter (except for post heavy-bombardment impacts), and 4) smooth intercrater plains. The involvement of water in these modification processes seems unavoidable, but interpretations of the surface conditions on early Mars range from the extremes of: 1) the "cold" model which envisions a thin atmosphere and surface temperatures below freezing except for local hydrothermal springs; and 2) the "warm" model, which invokes a thick atmosphere, seasonal temperatures above freezing in temperate and equatorial regions, and at least occasional precipitation as part of an active hydrological cycle. The nature of hydrologic cycles, if they occurred on Mars, would have been critically dependent on the environment. The resolution of where along this spectrum the actual environment of early Mars occurred is clearly a major issue, particularly because the alternate scenarios have much different implications about the possibility that life might have evolved on Mars. Additional information is contained in the original extended abstract.

Moore, J. M.↗

Manganese, Metallogenium, and Martian Microfossils

Manganese could easily be considered an abundant element in the Martian regolith, assuming that the composition of martian meteorites reflects the composition of the planet. Mineralogical analyses of 5 SNC meteorites have revealed an average manganese oxide concentration of 0.48%, relative to the 0.1% concentration of manganese found in the Earth's crust. On the Earth, the accumulation of manganese oxides in oceans, soils, rocks, sedimentary ores, fresh water systems, and hydrothermal vents can be largely attributed to microbial activity. Manganese is also a required trace nutrient for most life forms and participates in many critical enzymatic reactions such as photosynthesis. The wide-spread process of bacterial manganese cycling on Earth suggests that manganese is an important element to both geology and biology. Furthermore, there is evidence that bacteria can be fossilized within manganese ores, implying that manganese beds may be good repositories for preserved biomarkers. A particular genus of bacteria, known historically as Metallogenium, can form star-shaped manganese oxide minerals (called metallogenium) through the action of manganese oxide precipitation along its surface. Fossilized structures that resemble metallogenium have been found in Precambrian sedimentary formations and in Cretaceous-Paleogene cherts. The Cretaceous-Paleogene formations are highly enriched in manganese and have concentrations of trace elements (Fe, Zn, Cu, and Co) similar to modern-day manganese oxide deposits in marine environments. The appearance of metallogenium-like fossils associated with manganese deposits suggests that bacteria may be preserved within the minerals that they form. Additional information is contained in the original extended abstract.

Stein, L. Y.↗

Topographic Evaluation of Mars 2001 Candidate Landing Sites: A MGS-Viking Synergistic Study

One of the greatest unresolved issues concerns the evolution of Mars early in its history; during the time period that accretion was winding down but the frequency of impacting debris was still heavy. Ancient cratered terrain that has only been moderately modified since the period of heavy bombardment covers about a quarter of the planet's surface but the environment during its formation is still uncertain. This terrain was dominantly formed by cratering. But unlike on the airless Moon, the impacting craters were strongly modified by other contemporary surface processes that have produced distinctive features such as 1) dendritic channel networks, 2) rimless, flatfloored craters, 3) obliteration of most craters smaller than a few kilometers in diameter (except for post heavy-bombardment impacts), and 4) smooth intercrater plains. The involvement of water in these modification processes seems unavoidable, but interpretations of the surface conditions on early Mars range from the extremes of 1) the "cold" model which envisions a thin atmosphere and surface temperatures below freezing except for local hydrothermal springs; and 2) the "warm" model, which invokes a thick atmosphere, seasonal temperatures above freezing in temperate and equatorial regions, and at least occasional precipitation as part of an active hydrological cycle. The nature of hydrologic cycles, if they occurred on Mars, would have been critically dependent on the environment. The resolution of where along this spectrum the actual environment of early Mars occurred is clearly a major issue, particularly because the alternate scenarios have much different implications about the possibility that life might have evolved on Mars.

Moore, J. M.↗

Geology of McLaughlin Crater, Mars: A Unique Lacustrine Setting with Implications for Astrobiology

McLaughlin crater is a 92-kmdiameter Martian impact crater that contained an ancient carbonate- and clay mineral-bearing lake in the Late Noachian. Detailed analysis of the geology within this crater reveals a complex history with important implications for astrobiology [1]. The basin contains evidence for, among other deposits, hydrothermally altered rocks, delta deposits, deep water (>400 m) sediments, and potentially turbidites. The geology of this basin stands in stark contrast to that of some ancient basins that contain evidence for transient aqueous processes and airfall sediments (e.g. Gale Crater [2-3]).

Michalski, J. R.↗

Analyzers Measure Greenhouse Gases, Airborne Pollutants

In complete darkness, a NASA observatory waits. When an eruption of boiling water billows from a nearby crack in the ground, the observatory s sensors seek particles in the fluid, measure shifts in carbon isotopes, and analyze samples for biological signatures. NASA has landed the observatory in this remote location, far removed from air and sunlight, to find life unlike any that scientists have ever seen. It might sound like a scene from a distant planet, but this NASA mission is actually exploring an ocean floor right here on Earth. NASA established a formal exobiology program in 1960, which expanded into the present-day Astrobiology Program. The program, which celebrated its 50th anniversary in 2010, not only explores the possibility of life elsewhere in the universe, but also examines how life begins and evolves, and what the future may hold for life on Earth and other planets. Answers to these questions may be found not only by launching rockets skyward, but by sending probes in the opposite direction. Research here on Earth can revise prevailing concepts of life and biochemistry and point to the possibilities for life on other planets, as was demonstrated in December 2010, when NASA researchers discovered microbes in Mono Lake in California that subsist and reproduce using arsenic, a toxic chemical. The Mono Lake discovery may be the first of many that could reveal possible models for extraterrestrial life. One primary area of interest for NASA astrobiologists lies with the hydrothermal vents on the ocean floor. These vents expel jets of water heated and enriched with chemicals from off-gassing magma below the Earth s crust. Also potentially within the vents: microbes that, like the Mono Lake microorganisms, defy the common characteristics of life on Earth. Basically all organisms on our planet generate energy through the Krebs Cycle, explains Mike Flynn, research scientist at NASA s Ames Research Center. This metabolic process breaks down sugars for energy to fuel cellular functions. "We think this chemical process did not exist when life first formed on Earth," he says, "because it is based on oxygen being available, and there was little oxygen available on the early Earth." It is possible that there are anaerobic regions beneath the sea floor in which life forms like those early non-Krebs Cycle microbes may yet exist. To detect and potentially collect samples of life emerging from hydrothermal vents, Flynn and his colleagues created Medusa, a multi-sensor instrument designed for long-term observation of diked vents on the ocean floor. When the vents erupt, Medusa assesses indicators of life within the expelled water. If the results are positive, the observatory collects samples and detaches from the ocean floor, making the long journey to the surface for retrieval by scientists. One of the indicators Medusa measures is the ratio of carbon isotopes in the water, namely carbon-12 and carbon-13. Living organisms preferentially take up carbon-12, Flynn says, so examining the ratio of these isotopes can help to determine the source of carbon in an environment as either biological or non-biological. "On Mars, there is evidence of localized methane in the atmosphere, and that methane could come from biological sources or from geochemical ones," Flynn says. "Determining the background planetary carbon isotope ratios and then evaluating the specific carbon ratios in this methane would help to determine how it was formed." A long-duration observatory similar to Medusa could one day provide essential evidence for or against the presence of life on the Red Planet or beneath the ice-crusted oceans of Europa.

Source record↗

Kinetics of D/H isotope fractionation between molecular hydrogen and water

At equilibrium, the D/H isotope fractionation factor between H 2 and H 2 O (α H 2 O-H 2 (eq) ) is a sensitive indicator of temperature, and has been used as a geothermometer for natural springs and gas discharges. However, δD H 2 measured in spring waters may underestimate subsurface temperatures of origin due to partial isotopic re-equilibration during ascent and cooling. In this work, we present new experimental data on the kinetics of D–H exchange for H 2 dissolved in liquid water at temperatures below 100 °C. Comparing these results with published exchange rates obtained from gas phase experiments (100–400 °C), we derive a consistent activation energy of 52 kJ/mol, and the following rate expressions; ln k =9.186 - 6298/ T and k 1 = 9764.61[H 2 O] e-6298/ T where T is absolute temperature (K), k is the universal rate constant ([L/mol]/hr), and k 1 is a pseudo-first-order constant (hr -1 ) applicable to water-dominated terrestrial systems by constraining [H 2 O] as the density of H 2 O (in mol/L) at the P-T of interest. The density-dependent rate constant accounts for the kinetic disparity of D–H exchange with H 2 when dissolved in liquid H 2 O relative to a gas/steam phase, exemplifed by 1/ k 1 at 100 °C of ~2 days in liquid, versus ~7 yrs in saturated steam. This difference may explain the high variability of δDH 2 observed in fumarolic gases. Fluids convecting in the crust frequently reach T > 225 °C, where isotopic equilibrium is rapidly attained (<1 hr). We compare fractionation factors measured in natural fluids (α OBS ) with values expected for equilibrium at the T of acquisition. Where these values differ, we use kinetic models to estimate cooling rates during upward advection that account for the observed disequilibrium. Models fit to fluids from Yellowstone Park and the Lost City (deep-sea) vent field, both recovered at ~90 °C, require respective transit times of ~7 hrs and ~11 days between higher temperature reaction zones and the surface. Using estimates of subsurface depths of origin, however, suggests similar mean fluid flow rates (10 s of meters/hr). Additional complications must be considered when interpreting the δDH 2 of lower-temperature effluent. When applied to data from deep-sea hydrothermal systems, our kinetic models indicate microbial catalysis accelerates D–H exchange once fluids cool below ~60 °C. The H 2 measured in both continental alkaline springs and fracture fluids from Precambrian shield rock is likely produced at T < 100 °C, through processes such as serpentinization. In these settings, δDH 2 values appear closer to equilibrium with H 2 O than those from geothermal systems. Considering kinetic isotope effects may yield H 2 that is out of equilibrium when generated at lower temperatures, we calculate maximum (isothermal) times to apparent isotopic equilibrium of 1.3 yrs at 50 °C, 9 yrs at 25 °C, and 35 yrs at 10 °C. A similar calculation applied to Antarctic brines (-13 °C), where measured δDH 2 is far from equilibrium, yields ~350 yrs. This time is shorter than the fluids have been isolated (2.8 ka), suggesting kinetic isotope effects associated with H 2 destruction or loss via diffusion may also be possible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrothermal discharge from the El Tatio basin, Atacama, Chile

El Tatio in northern Chile is one of the best-studied geothermal fields in South America. However, there remain open questions about the mass and energy budgets, water recharge rates and residence time in the subsurface, origin of dissolved solutes, and processes affecting the phase and chemical composition of groundwater and surface water. Here we measured and sampled surface manifestations of the geothermal system (geysers, perpetual spouters, mud pools/volcanoes, and non-eruptive hot springs) and meteoric water. From the isotopic composition we infer that the thermal water has a meteoric origin that is different from the composition of local meteoric water. The absence of detectable tritium in thermal waters indicates that most of the recharge occurred pre-1950. Boiling and steam separation from the deep reservoir appear to be the main subsurface processes affecting the thermal fluids. A large amount of heat is lost to the atmosphere by evaporation from surface water and by steam emitted from erupting geysers. Finally, using the chloride inventory method, we estimate thermal water discharge to be 218 to 234 L/s, and the advective heat flow to be 120 to 170 MW.

15 GEOTHERMAL ENERGY↗

Detection of Crystalline Hematite Mineralization on Mars by the Thermal Emission Spectrometer: Evidence for Near-surface Water

The Thermal Emission Spectrometer (TES) instrument on the Mars Global Surveyor (MGS) mission has discovered a remarkable accumulation of crystalline hematite ((alpha-Fe2O3) that covers an area with very sharp boundaries approximately 350 by 350-750 km in size centered near 2 S latitude between 0 and 5 W longitude (Sinus Meridiani). Crystalline hematite is uniquely identified by the presence of fundamental vibrational absorption features centered near 300, 450, and >525/cm, and by the absence of silicate fundamentals in the 1000/cm region. Spectral features resulting from atmospheric CO2, dust, and water ice were removed using a radiative transfer model. The spectral properties unique to Sinus Meridiani were emphasized by removing the average spectrum of the surrounding region. The depth and shape of the hematite fundamental bands show that the hematite is crystalline and relatively coarse grained (>5-10 micron). Diameters up to and greater than 100s of micrometers are permitted within the instrumental noise and natural variability of hematite spectra. Hematite particles <5-10 micron in diameter (either as an unpacked or hard-packed powders) fail to match the TES spectra. The spectrally-derived areal abundance of hematite varies with particle size from approximately 10% for particles >30 micron in diameter to 40-60% for unpacked 10 micron powders. The hematite in Sinus Meridiani is thus distinct from the fine-grained (diameter <5-10 micron), red, crystalline hematite considered, on the basis of visible, near-IR data, to be a minor spectral component in Martian bright regions like Olympus-Amazonis. Sinus Meridiani hematite is closely associated with a smooth, layered, friable surface that is interpreted to be sedimentary in origin. This material may be the uppermost surface in the region, indicating that it could be a late-stage sedimentary unit, or it could be a layered portion of the heavily cratered plains units. We consider five possible mechanisms for the formation of coarse-grained, crystalline hematite. These processes fall into two classes depending on whether they require a significant amount of near-surface water: (1) chemical precipitation that includes origin by (a) precipitation from oxygenated, Fe-rich water (iron formations), (b) hydrothermal extraction and crystal growth.

Christensen, P. R.↗

Robotic Planning under Uncertainty in Spatiotemporal Environments in Expeditionary Science

In the expeditionary sciences, spatiotemporally varying environments -- hydrothermal plumes, algal blooms, lava flows, or animal migrations -- are ubiquitous. Mobile robots are uniquely well-suited to study these dynamic, mesoscale natural environments. We formalize expeditionary science as a sequential decision-making problem, modeled using the language of partially-observable Markov decision processes (POMDPs). Solving the expeditionary science POMDP under real-world constraints requires efficient probabilistic modeling and decision-making in problems with complex dynamics and observational models. Previous work in informative path planning, adaptive sampling, and experimental design have shown compelling results, largely in static environments, using data-driven models and information-based rewards. However, these methodologies do not trivially extend to expeditionary science in spatiotemporal environments: they generally do not make use of scientific knowledge such as equations of state dynamics, they focus on information gathering as opposed to scientific task execution, and they make use of decision-making approaches that scale poorly to large, continuous problems with long planning horizons and real-time operational constraints. In this work, we discuss these and other challenges related to probabilistic modeling and decision-making in expeditionary science, and present some of our preliminary work that addresses these gaps. We ground our results in a real expeditionary science deployment of an autonomous underwater vehicle (AUV) in the deep ocean for hydrothermal vent discovery and characterization. Our concluding thoughts highlight remaining work to be done, and the challenges that merit consideration by the reinforcement learning and decision-making community.

Preston, Victoria↗

Application of thematic mapper-type data over a porphyry-molybdenum deposit in Colorado

The objective of the study was to evaluate the utility of thematic mapper data as a source of geologically useful information for mountainous areas of varying vegetation density. Much of the processing was done in an a priori manner without prior ground-based information. This approach resulted in a successfull mapping of the alteration associated with the Mt. Emmons molybdenum ore body as well as several other hydrothermal systems. Supervised classification produced a vegetation map at least as accurate as the mapping done for the environmental impact statement. Principal components were used to map zones of general, subtle alteration and to separate hematitically stained rock from staining associated with hydrothermal activity. Decorrelation color composites were found to be useful field mapping aids, easily delineating many lithologies and vegetation classes of interest. The factors restricting the interpretability and computer manipulation of the data are examined.

Rickman, D. L.↗

Early Evolution of Earth's Geochemical Cycle and Biosphere: Implications for Mars Exobiology

Carbon (C) has played multiple key roles for life and its environment. C has formed organics, greenhouse gases, aquatic pH buffers, redox buffers, and magmatic constituents affecting plutonism and volcanism. These roles interacted across a network of reservoirs and processes known as the biogeochemical C cycle. Changes in the cycle over geologic time were driven by increasing solar luminosity, declining planetary heat flow, and continental and biological evolution. The early Archean C cycle was dominated by hydrothermal alteration of crustal rocks and by thermal emanations of CO2 and reduced species (eg., H2, Fe(2+) and sulfides). Bioorganic synthesis was achieved by nonphotosynthetic CO2-fixing bacteria (chemoautotrophs) and, possibly, bacteria (organotrophs) utilizing any available nonbiological organic C. Responding both to abundant solar energy and to a longterm decline in thermal sources of chemical energy and reducing power, the blaspheme first developed anoxygenic photosynthesis, then, ultimately, oxygenic photosynthesis. O2-photosynthesis played a central role in transforming the ancient environment and blaspheme to the modem world. The geochemical C cycles of early Earth and Mars were quite similar. The principal differences between the modem C cycles of these planets arose during the later evolution of their heat flows, crusts, atmospheres and, perhaps, their blasphemes.

DesMarais, David J.↗

Evaluation of Engineered Barrier Systems FY20 Report

This report describes research and development (R&D) activities conducted during fiscal year 2020 (FY20) specifically related to the Engineered Barrier System (EBS) R&D Work Package in the Spent Fuel and Waste Science and Technology (SFWST) Campaign supported by the United States (U.S.) Department of Energy (DOE). The R&D activities focus on understanding EBS component evolution and interactions within the EBS, as well as interactions between the host media and the EBS. A primary goal is to advance the development of process models that can be implemented directly within the Generic Disposal System Analysis (GDSA) platform or that can contribute to the safety case in some manner such as building confidence, providing further insight into the processes being modeled, establishing better constraints on barrier performance, etc. The FY20 EBS activities involved not only modeling and analysis work, but experimental work as well. Despite delays to some planned activities due to COVID-19 precautions, progress was made during FY20 in multiple research areas and documented in this report as follows: (1) EBS Task Force: Task 9/FEBEX Modeling Final Report: Thermo-Hydrological Modeling with PFLOTRAN, (2) preliminary sensitivity analysis for the FEBEX in-situ heater test, (3) cement-carbonate rock interaction under saturated conditions: from laboratory to modeling, (4) hydrothermal experiments, (5) progress on investigating the high temperature behavior of the uranyl-carbonate complexes, (6) in-situ and electrochemical work for model validation, (7) investigation of the impact of high temperature on EBS bentonite with THMC modeling, (8) sorption and diffusion experiments on bentonite, (9) chemical controls on montmorillonite structure and swelling pressure, (10) microscopic origins of coupled transport processes in bentonite, (11) understanding the THMC evolution of bentonite in FEBEX-DP—coupled THMC modeling, (12) modeling in support of HotBENT, an experiment studying the effects of high temperatures on clay buffers/near-field, and (13) high temperature heating and hydration column test on bentonite.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hydrothermal synthesis of molybdenum trioxide, characterization and photocatalytic activity

Highlights: • α-MoO{sub 3} micro-belts were synthesized hydrothermally. • Micro-belts were found very rich in surface oxygen vacancies. • CR-F3BS photocatalytic degradation was promising. • The cytotoxicity and mutagenicity were reduced significantly of CR-F3BS. - Abstract: α-MoO{sub 3} micro-belts were synthesized via hydrothermal technique and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX) and particle size analyzer. Photo-catalytic activity was evaluated by degrading Coralene Red F3BS (CR-F3BS) dye and process variables i.e., pH, photocatalyst dose, concentration of CR-F3BS and UV exposure time were optimized using response surface methodology (RSM) under central composite design (CCD). Under optimized conditions, up to 95% degradation of CR-F3BS (10 mg/L) was achieved for 120 min UV irradiation time at pH 7 using 2.75 g/L catalyst dose. The obtained RSM model revealed a satisfactory correlation between experimental and predicted CR-F3BS degradation values. Ames and heamolytic tests revealed that the toxicity was reduced significantly as a result of photo-catalytic treatment. In view of promising efficiency, α-MoO{sub 3} micro-belts could possibly be used for the degradation of dyes in textile effluents.

36 MATERIALS SCIENCE↗

Thermal Equation of State of Natural Ti-Bearing Clinohumite

The natural occurrence of clinohumite in metabasalts and hydrothermally altered peridotites provides a source of water-rich minerals in subducted slabs, making knowledge of their phase relations and crystal chemistry under high pressure-temperature ( P - T ) conditions important for understating volatile recycling and geodynamic process in the Earth's mantle. Here we present a synchrotron-based, single-crystal X-ray diffraction study on two natural Ti-bearing clinohumites up to ~28 GPa and 750 K in order to simulate conditions within subducted slabs. No phase transition occurs in clinohumite over this P - T range. Pressure-volume relationships of both compositions at room temperature were fitted to a third-order Birch-Murnaghan equation of state (EoS) with V 0 = 650.4(3) Å 3 , K T 0 = 141(4) GPa, and K T 0 ' = 4.0(6) for Ti-poor clinohumite (0.07 Ti per formula unit, pfu) and V 0 = 650.8(3) Å 3 , K T 0 = 144(4) GPa, and K T 0 ' = 3.6(7) for Ti-rich clinohumite (0.21 Ti pfu). Both clinohumites exhibit anisotropic compression with β b > β c > β a . We also refined P-V-T equation of state parameters using the high-temperature Birch-Murnaghan EoS, yielding (∂ K T 0 /∂ T ) P = –0.040(10) GPa/K and α T = 5.1(6) × 10 -5 K -1 for Ti-poor clinohumite and (∂ K T 0 /∂ T ) P = –0.045(11) GPa/K and α T = 5.7(6) × 10 -5 K -1 for Ti-rich clinohumite. We report Ti-poor and Ti-rich clinohumites display similar equations of state but are ~20% more incompressible than Mg-pure clinohumite and display ~5% higher bulk sound velocity than olivine at upper mantle conditions. Our results provide constraints for modeling geodynamic process related to the subduction and transport of potentially water-rich slabs in the mantle.

58 GEOSCIENCES↗

Hydrothermal synthesis of bismuth niobates and their application in azo-dyes photo-discoloration

Highlights: • A new method of synthesis for obtaining pure phase bismuth niobates is proposed. • α-BiNbO{sub 4} and β-BiNbO{sub 4} were obtained by the calcination of an amorphous precursor. • Nanosized bismuth niobates have shown high band gap energies (3.2–3.4 eV). • Bismuth niobates are very efficient in the photo-discoloration of methyl orange. - Abstract: Bismuth niobates were obtained by hydrothermal synthesis using bismuth (III) nitrate pentahydrate [Bi(NO{sub 3}){sub 3}·5H{sub 2}O] and a Lindqvist potassium hexaniobate [K{sub 8-x}H{sub x}Nb{sub 6}O{sub 19}.nH{sub 2}O] as soluble precursors. Pure crystalline Bi{sub 5}Nb{sub 3}O{sub 15}, β-BiNbO{sub 4} and α- BiNbO{sub 4} were obtained as pure phases through co-precipitation at pH = 8, followed by hydrothermal treatment and calcination at 600, 700 or 800 °C, respectively, which are milder temperatures than those used in solid state, citrate sol-gel and ball milling methods. Band gap energies of α-BiNbO{sub 4} and β-BiNbO{sub 4} were estimated by UV–vis diffuse reflectance spectroscopy (DRS) as 3.2–3.4 eV, which are higher than experimental values reported in the literature. The materials were evaluated in the methyl orange azo-dye photo-discoloration under UV irradiation and complete bleach was attained. The triclinic phase presented a better efficiency as a photocatalyst than the orthorhombic phase. Unexpectedly, the mixture of both phases resulted in the highest photocatalytic efficiency, similar to that found for Degussa P25 commercial catalyst.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗