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At least 559 records · Page 31

Heterogeneous photo-Fenton-like degradation of emerging pharmaceutical contaminants in wastewater using Cu-doped MgO nanoparticles

In this study, a facile thermal decomposition method was utilized to synthesize Cu-doped MgO nanoparticles possessing mesoporosity. These mesoporous Cu doped MgO nanoparticles were shown to be efficient photo-Fenton-like catalysts for the degradation of emerging pharmaceutical contaminants in wastewater and were able to completely oxidize salicylic acid within 1 hour under optimized conditions. Tetracycline was shown to be converted to other intermediates with a large portion of it undergoing full mineralization. Batch experiments were conducted to demonstrate the effects of Cu loading on MgO, overall catalyst loading, and H 2 O 2 concentration on the salicylic acid and tetracycline conversion and rate constants. Quenching experiments revealed that both •OH radicals or HO 2 •/•O 2 - radicals were involved in the reaction, with the latter showing a higher contribution. The surface dissolution of MgO was shown to facilitate a high pH environment which completely prevented Cu from leaching out of the catalyst while retaining high activity. The catalyst reusability was shown to be satisfactory with high activity and conversion being preserved over five cycles.

04 OIL SHALES AND TAR SANDS↗

Simple but tricky: Investigations of terephthalic acid purity obtained from mixed PET waste

In this study, we report for the first time, the basic depolymerization of mixed waste-polyethylene terephthalate (PET) by hydrolysis and subsequent terephthalic acid monomer recovery at high purity using benign reaction conditions. Several conditions were tested for depolymerization such as PET chips size, concentration of aqueous sodium hydroxide (20 or 30%), organic co-solvent (ethylene glycol or ethanol), temperature at which the reaction was run and duration of the heating. More importantly, several batches of PET were utilized as starting materials including a commercial PET, chopped PET obtained from clean bottles whose caps and labels were removed and the purity of the product from each condition was evaluated via nuclear magnetic resonance (1HNMR and 13CNMR), differential scanning calorimetry (DSC) and powder Xray diffraction (XRD). Unsurprisingly, the conversion of PET is dependent on the particle size varying from 100% conversion for fine powder to 73% conversion for (300 µm, mesh 6 – 20 or mesh 14-20). Ethanol appears to be more efficient as a co-solvent than ethylene glycol, with higher PET depolymerization conversions (94% versus 75-80%), shorter reaction times (2h versus 6h) and lower temperatures (80 °C versus 110 °C). The terephthalic acid (TPA) recovered appeared to have only subtle differences among the batches, most notably a pink color when the reaction was run in ethanol/base. The DSC of the compounds produced in ethylene glycol water appear to display a melting point (280-288 °C) while the samples prepared in ethanol as well as a commercial sample did not. Overall, the purity of the various TPA batches is comparable, and similar to commercial TPA, demonstrating the utility of the method to depolymerize realistic waste streams. The method is simple, demonstrated on multigram scale (15-30g) and allows for the complete removal of waste other than PET unaffected by alkaline conditions.

Cosimbescu, Lelia↗

Customizable Aperture Geometry in Metal–Organic Frameworks for Kinetic Hydrocarbon Separation

Precise control of aperture dimensions is crucial in adsorptive separations of hydrocarbons, as it directly affects key parameters such as selectivity, capacity, diffusion, and recyclability. The development of metal–organic frameworks (MOFs) has enabled the fine-tuning of local pore environments to address important hydrocarbon separations. However, customizing the aperture geometry to tune the kinetic separation performance remains challenging. Here, we deploy a mixed-linker synthesis strategy, combining long and short linkers on fcu net Zr-MOFs with equilateral triangular apertures to construct isoreticular multivariate MOFs, NU-415 and NU-416, with tailored isosceles triangular apertures suitable for the separation of hexane isomers. Sorption, liquid batch separation, and X-ray diffraction measurements demonstrate significantly improved selectivity, capacity, stability, and recyclability of NU-415 and NU-416 compared with Zr-muconate and MOF-801. Notably, both NU-415 and NU-416 achieve uptake capacities of 2.2 mmol g –1 in 1 min with an n-hexane to 2,2-dimethylbutane selectivity over 200 in an equimolar ternary mixture at ambient conditions, comparable to leading reported materials. Mechanistic studies confirm that separation performance is predominantly governed by significant kinetic differences rather than by thermodynamics. Furthermore, the successful customization of aperture geometry not only enables superior linear to monobranched hexane selectivity in NU-415 but also demonstrates the mixed-linker synthesis strategy as a promising solution for precise and predictable pore architecture control in MOFs.

Adsorption↗

Navigation strategy and filter design for solar electric missions

Methods which have been proposed to improve the navigation accuracy for the low-thrust space vehicle include modifications to the standard Sequential- and Batch-type orbit determination procedures and the use of inertial measuring units (IMU) which measures directly the acceleration applied to the vehicle. The navigation accuracy obtained using one of the more promising modifications to the orbit determination procedures is compared with a combined IMU-Standard. The unknown accelerations are approximated as both first-order and second-order Gauss-Markov processes. The comparison is based on numerical results obtained in a study of the navigation requirements of a numerically simulated 152-day low-thrust mission to the asteroid Eros. The results obtained in the simulation indicate that the DMC algorithm will yield a significant improvement over the navigation accuracies achieved with previous estimation algorithms. In addition, the DMC algorithms will yield better navigation accuracies than the IMU-Standard Orbit Determination algorithm, except for extremely precise IMU measurements, i.e., gyroplatform alignment .01 deg and accelerometer signal-to-noise ratio .07. Unless these accuracies are achieved, the IMU navigation accuracies are generally unacceptable.

Tapley, B. D.↗

Ruled and holographic experiment (AO 138-5)

The AO 138-5 experiment was designed, via the FRECOPA (FRench COoperative PAyload) experiment with the aim to study the optical behavior of different diffraction gratings submitted to space vacuum long exposure and solar irradiation. Samples were ruled and holographic gratings, masters or replica, and some additional control mirrors with various coatings. The experiment was located on the B3, trailing edge of the LDEF and was protected against Atomic Oxygen flux. The experienced thermal cycling was evaluated from -23 C to 66 C during the flight, 34,000 orbits. The samples (two batches of four pieces) were located on a dedicated plate, by a pair of equivalent gratings or mirrors; optical faces were located on the external side. The plate was inside a canister, which had been opened in space for ten months. When the satellite returned to Kennedy Space Center, the remaining vacuum in the canister was still correct. The analysis focused on the triple point characterization including light efficiency, wavefront flatness quality and stray light level. Tests were conducted on control mirrors and gratings (rules and holographic master or replica) loaded but not exposed to cosmic dust or direct solar irradiations. They did not show any significant variations. Solar exposure had damaged the coating (aluminum and platinum) reflectivity in the Ultra-Violet region; the degradation is higher with the gratings, in terms of efficiency. However, wavefront flatness quality and stray light level tests revealed no additional changes.

Bonnemason, Francis↗

Mechanisms and kinetics of citrate-promoted dissolution of a uranyl phosphate mineral

The formation of uranyl phosphate precipitates is a remediation strategy to limit the mobility of uranium in contaminated soils. However, exposure to organic ligands, like the plant exudate citrate, can remobilize the uranium. The purpose of this study is to provide a more thorough comprehension of citrate-promoted dissolution of a uranyl phosphate mineral, chernikovite [(H 3 O)(UO 2 )(PO 4 )·3H 2 O], by determining the extent of uranium release from chernikovite at a wide range of citrate concentrations. Here we have quantified the kinetics of dissolution and proposed potential mechanisms of chernikovite dissolution to gain a better understanding of the fate of uranyl phosphate precipitates in the environment. Batch dissolution and continuously stirred tank reactor (CSTR) experiments indicate that increasing citrate concentrations from 0.1 mM to 50 mM increases the concentration of dissolved uranium. However, at citrate concentrations of 10 mM and greater, the effectiveness of the ligand to enhance the dissolution decreases. Density functional theory modeling and Raman spectroscopy indicate a strong interaction between citrate and the uranyl ions at the surface of the uranyl phosphate. The interaction between citrate and uranyl suggests the formation of an alteration layer of uranyl-citrate surface complexes, which could impede uranium release at citrate concentrations of 10 mM or higher. Together, these results indicate that the citrate-promoted dissolution of chernikovite is a fast reaction that is hindered by a combination of surface saturation and a secondary-phase precipitation reaction at higher concentrations of citrate and reaction times greater than or equal to 72 min based on the hydraulic residence time of CSTR experiments. These findings improve our understanding of the stability of uranyl phosphate for use in sequestration of uranium groundwater plumes at contaminated sites.

58 GEOSCIENCES↗

Data-Driven Discovery of Bimetallic Nanoparticles Catalysts for the Hydrogenolysis of Polyethylene

Supported platinum nanoparticles are known to convert polyolefins to high-quality liquid hydrocarbons with hydrogen under relatively mild conditions. However, no systematic study has been undertaken using bimetallic catalysts for polyethylene upcycling. Specifically, a total of 98 monometallic and bimetallic combinations (Ag, Cr, Co, Cu, Fe, Ga, In, Mn, Ni, Pd, Pt, Rh, Ru, Zr) on alumina were synthesized utilizing surface organometallic chemistry (SOMC) technique via robotic platform. These were investigated at a small scale (10 mg of catalyst and 50 mg of polyethylene) for their activity for the hydrogenolysis of polyethylene in a high-throughput batch reactor. Combinations of Ni and Co were selected as candidates with high activity toward conversion into paraffin oils. Reaction conditions were optimized with Ni/Co/Al 2 O 3 catalyst at a larger scale (300 mg catalyst and 3 g polyethylene) to obtain a high yield (93.1%) of paraffin wax with desired properties (M n = 380 Da) and low polydispersity (Đ = 1.2). Ni/Co/Al 2 O 3 was compared against Co/Ni/Al 2 O 3 to understand the role of the deposition sequence. When Co is deposited before Ni, a layer of cobalt aluminate is formed upon reduction, stabilizing the deposition of 5 nm metallic Ni particles. When nickel is deposited before Co, particles are larger (average >20 nm) and more oxidized (Ni δ+ in NiAl 2 O 4 ), decreasing the availability of the catalytically active metallic Ni. In conclusion, the difference in electronic environments was also described by DFT calculations, which revealed that smaller 3D clusters of Ni are preferred on CoAl2O4 over the 3D clusters on NiAl 2 O 4 and that these smaller clusters are more reducible, as confirmed experimentally.

Polymer↗

The evaporation of various lubricant fluids in vacuum.

The weight-loss rate in vacuum of 18 lubricating liquids and greases is reported for temperatures up to 120 C. Eleven types of 'medium-viscosity' (20 to 52 centistokes at 40 C) fluids were studied. In addition, a variety of perfluoro ether liquids having viscosities of 350 to 500 centistokes at 40 C were investigated, as were some commercial greases based on these liquids. The results showed that a methylchlorophenyl silicone, a high-viscosity-index perfluoro ether research fluid, and a polyoctene have suitably low outgassing properties for long-term space applicaitons requiring a medium-viscosity lubricant. Perfluoro ether greases also displayed low outgassing, but batch-to-batch variation was great. Mass spectrometer measurements indicated that the outgassed species were characterized by much lower molecular weights than that expected for the liquids. This suggests that lubricant transfer techniques which rely on evaporation from a reservoir may not be desirable for long-term space applications.

Hamilton, D. B.↗

About Small Streams and Shiny Rocks: Macromolecular Crystal Growth in Microfluidics

We are developing a novel technique with which we have grown diffraction quality protein crystals in very small volumes, utilizing chip-based, microfluidic ("LabChip") technology. With this technology volumes smaller than achievable with any laboratory pipette can be dispensed with high accuracy. We have performed a feasibility study in which we crystallized several proteins with the aid of a LabChip device. The protein crystals are of excellent quality as shown by X-ray diffraction. The advantages of this new technology include improved accuracy of dispensing for small volumes, complete mixing of solution constituents without bubble formation, highly repeatable recipe and growth condition replication, and easy automation of the method. We have designed a first LabChip device specifically for protein crystallization in batch mode and can reliably dispense and mix from a range of solution constituents. We are currently testing this design. Upon completion additional crystallization techniques, such as vapor diffusion and liquid-liquid diffusion will be accommodated. Macromolecular crystallization using microfluidic technology is envisioned as a fully automated system, which will use the 'tele-science' concept of remote operation and will be developed into a research facility aboard the International Space Station.

vanderWoerd, Mark↗

Vortex entropy and superconducting fluctuations in ultrathin underdoped Bi 2 Sr 2 CaCu 2 O 8+x superconductor

Vortices in superconductors can help identify emergent phenomena but certain fundamental aspects of vortices, such as their entropy, remain poorly understood. Here, we study the vortex entropy in underdoped Bi 2 Sr 2 CaCu 2 O 8+x by measuring both magneto-resistivity and Nernst effect on ultrathin flakes (≤2 unit-cell). We extract the London penetration depth from the magneto-transport measurements on samples with different doping levels. It reveals that the superfluid phase stiffness p s scales linearly with the superconducting transition temperature T c , down to the extremely underdoped case. On the same batch of ultrathin flakes, we measure the Nernst effect via on-chip thermometry. Together, we obtain the vortex entropy and find that it decays exponentially with T c or p s . We further analyze the Nernst signal above T c in the framework of Gaussian superconducting fluctuations. The combination of electrical and thermoelectric measurements in the two-dimensional limit provides fresh insight into high temperature superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Science Issues Associated with the Use of a Microfluidic Chip Designed Specifically for Protein Crystallization

The Iterative Biological Crystallization team in partnership with Caliper Technologies has produced a prototype microfluidic chip for batch crystallization that has been designed and tested. The chip is designed for the mixing and dispensing of up to five solutions with possible variation of the recipe being delivered to two growth wells. Developments that have led to the successful on-chip crystallization of a few model proteins have required investigative insight into many different areas, including fluid mixing dynamics, surface treatments, quantification and fidelity of reagent delivery. This presentation will encompass the ongoing studies and data accumulated toward these efforts.

Holmes, Anna M.↗

An Inversion Analysis of Recent Variability in Natural CO2 Fluxes Using GOSAT and In Situ Observations

About one-half of the global CO2 emissions from fossil fuel combustion and deforestation accumulates in the atmosphere, where it contributes to global warming. The rest is taken up by vegetation and the ocean. The precise contribution of the two sinks, and their location and year-to-year variability are, however, not well understood. We use two different approaches, batch Bayesian synthesis inversion and variational data assimilation, to deduce the global spatiotemporal distributions of CO2 fluxes during 2009-2010. One of our objectives is to assess different sources of uncertainties in inferred fluxes, including uncertainties in prior flux estimates and observations, and differences in inversion techniques. For prior constraints, we utilize fluxes and uncertainties from the CASA-GFED model of the terrestrial biosphere and biomass burning driven by satellite observations and interannually varying meteorology. We also use measurement-based ocean flux estimates and two sets of fixed fossil CO2 emissions. Here, our inversions incorporate column CO2 measurements from the GOSAT satellite (ACOS retrieval, filtered and bias-corrected) and in situ observations (individual flask and afternoon-average continuous observations) to estimate fluxes in 108 regions over 8-day intervals for the batch inversion and at 3 x 3.75 weekly for the variational system. Relationships between fluxes and atmospheric concentrations are derived consistently for the two inversion systems using the PCTM atmospheric transport model driven by meteorology from the MERRA reanalysis. We compare the posterior fluxes and uncertainties derived using different data sets and the two inversion approaches, and evaluate the posterior atmospheric concentrations against independent data including aircraft measurements. The optimized fluxes generally resemble those from other studies. For example, the results indicate that the terrestrial biosphere is a net CO2 sink, and a GOSAT-only inversion suggests a shift in the global sink from the tropics south to the north relative to the prior and to an in-situ-only inversion. We also find a smaller terrestrial sink in higher-latitude northern regions in boreal summer of 2010 relative to 2009.

Carbon dioxide↗

Apatite geochemistry as a tool for understanding the petrogenesis of layered mafic-ultramafic rocks in the Bushveld Complex, South Africa

The sources of the magmas that formed the Rustenburg Layered Suite of the Bushveld Complex in South Africa remain debated, despite decades of research. Vertical and lateral variation in bulk rock and mineral separate Sr-Nd isotopic compositions, which generally indicate enriched sources, demonstrate that the layered sequence was formed by the emplacement of multiple batches of magma, crucially resulting in episodes of PGE-Cr-V mineralisation. The Lu-Hf isotope compositions of zircon are, however, at odds with the bulk rock Sr-Nd isotopic heterogeneity as they show near homogeneous compositions throughout the layered sequence (εHf (2.06 Ga) =−8). This lack of variation in Hf isotope composition has been attributed to deep, continental lithospheric mantle-related and/or crustal contamination of plume-derived Bushveld magmas. In this study, we analysed the major, trace element and Sr-Nd isotope geochemistry of apatite in the Rustenburg Layered Suite. Apatite occurs as an intercumulus mineral in the lowermost regions and a cumulus mineral in the uppermost regions of the layered sequence and can therefore be used to test existing models for the isotopic disequilibrium between bulk rock Sr-Nd and zircon Hf isotopic compositions. Apatite is largely chlorapatite in the lowermost regions and fluorapatite in the uppermost regions of the layered sequence. The Merensky Reef is unusual in that it comprises both chlorapatite and fluorapatite. Apatite throughout the layered sequence is generally unzoned and shows no evidence of late-stage alteration. Trace element data show that apatite is enriched in L/HREE, with common negative Eu-Sr anomalies. These trace element signatures are consistent with a magmatic origin for the apatite grains, with prior, or concurrent, plagioclase crystallization from the same melt. Variability in in situ Sr and Nd isotope compositions of apatite is recorded throughout the layered sequence with εNd (2.06 Ga) compositions varying between −2.5 and − 10.2 and initial 87 Sr/ 86 Sr compositions varying between 0.7079 and 0.7103 (for the Marikana dikes only). The variability in Sr-Nd isotope compositions of apatite is consistent with the bulk rock (and mineral separate) variation in Sr-Nd isotope compositions, suggesting apatite preserves primary magmatic compositions in the Rustenburg Layered Suite.

Apatite↗

Soil viral production count, respiration, and amplicon data

This study aimed to quantify rates of viral production in aridisol soil under conditions as close to natural field soil as possible given the perturbations necessary to manipulate viral abundances. Viruses were removed from soil, then added back to virus-depleted soil to control the initial viral abundances at either 100% (field_abund) or 10% (reduced_abund) of measured field viral abundance to generate treatments with field-relevant and reduced viral infection pressure, respectively. Replicates of batch incubation jars were harvested every 8 hours for 48 hours to enumerate bacteria and viruses by microscopy (n=5) and profile bacterial community composition by 16S rRNA amplicon sequencing (n=3).

Zimmerman, Amy [Pacific Northwest National Laborat↗

RINA: An interactive system for the rapid interpretation of NASTRAN results

RINA is a general post-processor system which performs data reduction, post processing and post analysis of NASTRAN results. RINA can be run in either batch or time-sharing mode. The system, which is an expansion of the NASDAT program, performs the following tasks: (1) scan of extreme values for displacements, forces, stresses and margins of safety, (2) computations of envelopes for displacements, forces, stresses and margins of safety, (3) computations of allowables and margins of safety; and (4) generation of NASTRAN tables needed for reanalysis computations. Usage of all these options provides the analyst with an efficient tool for the study and interpretation of NASTRAN analysis results and their presentation for project documentation.

Raibstone, A. I.↗

First results from analysis of coordinated AVIRIS, TIMS, and ISM (French) data for the Ronda (Spain) and Beni Bousera (Morocco) peridotites

Ultramafic rocks are relatively rare at the Earth's surface but constitute the vast majority of the Earth by volume. Exposures of ultramafic bodies are therefore crucial for deducing many important processes that occur in the Earth's mantle. An important science question regarding the spatial distribution, abundance, and composition of mafic minerals in ultramafic bodies that can be examined with advanced sensor data is the melting process. When a lherzolite melts, clinopyroxene (cpx) melts first and therefore variations in the modal amount of cpx remaining in the mantle are a reflection of the amount of fractional melting that has occurred. Fe goes preferentially into the melt during melting but a 20 percent batch melting (i.e. closed system) acquires less Fe relative to 20 percent fractional melting (i.e. open system). Since the strength and wavelength of diagnostic absorptions is a strong function of Fe content, it is possible to make maps of the variation in Fe:Mg ratios which can be related to the general melting process. Accurate ground-truth information about local mineralogy provides internal calibration and consistency checks. Investigations using imaging spectrometer are very complementary to field studies because advanced sensor data can provide a synoptic view of modal mineralogy and chemical composition whereas field studies focus on detailed characterization of local areas. Two excellent exposures of ultramafic lithologies are being investigated with visible to mid-infrared imaging spectrometer data: the Ronda peridotite near Ronda, Spain and the Beni Bousera ophiolitic fragment in northern Morocco. Although separated by the Alboran Sea, these bodies are thought to be related and represent fertile sub-continental mantle. The Ronda peridotite is predominantly spinel lherzolite but grades into harzburgite and shows considerable variation in major and trace element compositions. Mafic layering and dykes (i.e. olivine gabbro) are also observed. This indicates some sections of the peridotite have experienced greater degrees of partial melting. The Beni Bousera peridotite also contains mafic layers and dykes and grades into harzburgite representing similar fundamental shifts in the bulk chemistry of this ultramafic body probably related to an episode of partial melting. The specific mode of emplacement of these bodies is controversial and important for understanding the tectonic evolution of this region. Our investigations are not necessarily designed to help resolve this controversy. Rather, these exposures provide excellent and unusual examples of fertile mantle which have undergone variable degrees of partial melting.

Mustard, J. F.↗

Growth of carbon nanotube forests on flexible metal substrates: Advances, challenges, and applications

Owing to their remarkable properties and ordered architecture, vertically aligned CNT forests (VACNT) hold promises for countless applications ranging from energy storage to multifunctional fiber production. Over the last three decades, studies of carbon nanotube (CNT) growth have provided invaluable insight into the CNT nucleation and growth mechanism and enabled critical advancements in nanotechnology. Nevertheless, the ability to fully harness the exceptional VACNT properties in commercial devices is bottlenecked by compatibility of current CNT synthesis processes with large-scale manufacturing. Metal foil substrates present an economic alternative to traditional insulating substrates, like silicon or quartz, and are compatible with both roll-to-roll and automated, large-scale, batch processes. Compared to CNT growth on Si substrates, metal foils present additional challenges, such as increased roughness and reactivity at high temperatures. Nonetheless, many successful VACNT growths on conducting metal foils have been reported, which demonstrate the feasibility of metal substrate use for large-volume production of high-quality CNTs. Here, in this review, we discuss advancements in the field of VACNT growth on metal foil and specifically examine different choices for metal substrates, barrier and catalyst layers, deposition and growth methods, resulting CNT characteristics, and highlight a number of applications that benefit from CNT growth on metal substrates and transition to large-scale manufacturing.

36 MATERIALS SCIENCE↗

Black Liquor Valorization by Using Marine Protist Thraustochytrium striatum and the Preliminary Metabolic Mechanism Study

Black liquor that contains various phenolic compounds from lignin solubilization has been the main byproduct of alkaline pretreatment of lignocellulosic biomass in the biorefinery. In this study, black liquor from alkaline pretreatment of corn stover was used as a sole carbon source for the cultivation of a marine protist, Thraustochytrium striatum. It was found that this strain can grow on black liquor and accumulate valuable products (e.g., fatty acids and carotenoids) simultaneously. Under optimal conditions (pH = 7 and NH 4 Cl = 2 g/L), the cell mass concentration reached 5.2 g/L with total aromatics decreased from 8.18 to 3.09 g/L within 7 day incubation. Fed-batch cultivation was adopted to increase the contents of total fatty acids and carotenoids to 13% and 0.24 mg/g dry cell mass, respectively. Although various compounds such as sugars and organic acids were detected in black liquor and consumed during microbial fermentation as carbon sources, lignin-derived compounds were identified as the major substrates for T. striatum fermentation. Of total aromatics consumed, monomers including p-coumaric acid, ferulic acid, vanillin, and syringaldehyde were observed to be consumed and converted while polymeric fragments were also depolymerized and degraded. Under optimal conditions, around 50% of the total aromatics was consumed. The dynamic changes of compounds in black liquor indicated that diverse metabolic processes were involved in black liquor degradation and utilization by T. striatum. A strong adaptation of T. striatum to a wide range of pH (3–9) was also observed during black liquor fermentation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗