110 research outputs found
Nitrate Pathways, Processes, and Timing in an Agricultural Karst System: Development and Application of a Numerical Model
An edited version of this paper was published by AGU. Copyright 2019 American Geophysical Union.Nitrogen (N) contamination within agricultural‐karst landscapes and aquifers is widely reported; however, the complex hydrological pathways of karst make N fate difficult to ascertain. We developed a hydrologic and N numerical model for agricultural‐karst, including simulation of soil, epikarst, phreatic, and quick flow pathways as well as biochemical processes such as nitrification, mineralization, and denitrification. We tested the model on four years of nitrate (NO3−) data collected from a phreatic conduit and an overlying surface channel in the Cane Run watershed, Kentucky, USA. Model results indicate that slow to moderate flow pathways (phreatic and epikarst) dominate the N load and account for nearly 90% of downstream NO3− delivery. Further, quick flow pathways dilute NO3− concentrations relative to background aquifer levels. Net denitrification distributed across soil, epikarst, and phreatic water removes approximately 36% of the N inputs to the system at rates comparable to nonkarst systems. Evidence is provided by numerical modeling that NO3− accumulation via evapotranspiration in the soil followed by leaching through the epikarst acts as a control on spring NO3− concentration and loading. Compared to a fluvial‐dominated immature karst system, mature‐karst systems behave as natural detention basins for NO3−, temporarily delaying NO3− delivery to downstream waters and maintaining elevated NO3− concentrations for days to weeks after hydrologic activity ends. This study shows the efficacy of numerical modeling to elucidate complex pathways, processes, and timing of N in karst systems
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Tailor-made nanostructures bridging chaos and order for highly efficient white organic light-emitting diodes
Organic light-emitting diodes (OLEDs) suffer from notorious light trapping, resulting in only moderate external quantum efficiencies. Here, we report a facile, scalable, lithography-free method to generate controllable nanostructures with directional randomness and dimensional order, significantly boosting the efficiency of white OLEDs. Mechanical deformations form on the surface of poly(dimethylsiloxane) in response to compressive stress release, initialized by reactive ions etching with periodicity and depth distribution ranging from dozens of nanometers to micrometers. We demonstrate the possibility of independently tuning the average depth and the dominant periodicity. Integrating these nanostructures into a two-unit tandem white organic light-emitting diode, a maximum external quantum efficiency of 76.3% and a luminous efficacy of 95.7 lm W−1 are achieved with extracted substrate modes. The enhancement factor of 1.53 ± 0.12 at 10,000 cd m−2 is obtained. An optical model is built by considering the dipole orientation, emitting wavelength, and the dipole position on the sinusoidal nanotexture
The influence of reaction conditions on the oxidation of cyclohexane via the in-situ production of H2O2
The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), both key materials in the production of Nylon. Herein we demonstrate that through the in-situ production of H2O2 supported AuPd nanoparticles catalyse the formation of KA oil under conditions where activity is limited when using molecular O2, with no loss in catalytic activity observed upon re-use. The effect of key reaction parameters, including reaction temperature, catalyst mass and H2:O2 ratio are evaluated
Stochastic Pulse Switching in a Degenerate Resonant Optical Medium
Using the idealized integrable Maxwell-Bloch model, we describe random
optical-pulse polarization switching along an active optical medium in the
Lambda-configuration with disordered occupation numbers of its lower energy
sub-level pair. The description combines complete integrability and stochastic
dynamics. For the single-soliton pulse, we derive the statistics of the
electric-field polarization ellipse at a given point along the medium in closed
form. If the average initial population difference of the two lower sub-levels
vanishes, we show that the pulse polarization will switch intermittently
between the two circular polarizations as it travels along the medium. If this
difference does not vanish, the pulse will eventually forever remain in the
circular polarization determined by which sub-level is more occupied on
average. We also derive the exact expressions for the statistics of the
polarization-switching dynamics, such as the probability distribution of the
distance between two consecutive switches and the percentage of the distance
along the medium the pulse spends in the elliptical polarization of a given
orientation in the case of vanishing average initial population difference. We
find that the latter distribution is given in terms of the well-known arcsine
law
A comparative study of palladium-gold and palladium-tin catalysts in the direct synthesis of H2O2
Herein we evaluate the promotive effect of Au and Sn incorporation into supported Pd nanoparticles for the direct synthesis of H2O2 from molecular H2 and O2. The introduction of both secondary metal modifiers was found to result in a significant enhancement in catalytic performance, although, in the case of the PdSn system, it was identified that relatively large quantities of the secondary metal were required to rival the activity observed over optimal Au-containing formulations, with the 0.25%Pd-2.25%Sn/TiO2 catalyst offering comparable H2O2 synthesis rates to the optimised 0.25%Pd-0.25%Au/TiO2 formulation. The introduction of Sn was found to considerably improve Pd dispersion, correlating with an improvement in selective H2 utilisation. Notably, the optimal PdSn catalyst identified in this work achieves superior H2O2 selectivities compared to the PdAu analogue and is able to rival the performance of state-of-the-art materials
Foliations of Isonergy Surfaces and Singularities of Curves
It is well known that changes in the Liouville foliations of the isoenergy
surfaces of an integrable system imply that the bifurcation set has
singularities at the corresponding energy level. We formulate certain
genericity assumptions for two degrees of freedom integrable systems and we
prove the opposite statement: the essential critical points of the bifurcation
set appear only if the Liouville foliations of the isoenergy surfaces change at
the corresponding energy levels. Along the proof, we give full classification
of the structure of the isoenergy surfaces near the critical set under our
genericity assumptions and we give their complete list using Fomenko graphs.
This may be viewed as a step towards completing the Smale program for relating
the energy surfaces foliation structure to singularities of the momentum
mappings for non-degenerate integrable two degrees of freedom systems.Comment: 30 pages, 19 figure
The selective oxidation of cyclohexane via In-situ H2O2 production over supported Pd-based catalysts
The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), key materials in the production of Nylon. The in-situ route has the potential to overcome the significant economic and environmental concerns associated with the use of commercial H2O2, while also allowing for the use of far lower reaction temperatures than those typical of the purely aerobic route to KA oil. Herein we demonstrate the efficacy of a series of bi-functional Pd-based catalysts, which offer appreciable concentrations of KA oil, under conditions where limited activity is observed using O2 alone. In particular the introduction of V into a supported Pd catalyst is seen to improve KA oil concentration by an order of magnitude, compared to the Pd-only analogue. In particular we ascribe this improvement in catalytic performance to the development of Pd domains of mixed oxidation state upon V incorporation as evidenced through X-ray photoelectron spectroscopy
Cys-Ph-TAHA: a lanthanide binding tag for RDC and PCS enhanced protein NMR
Here we present Cys-Ph-TAHA, a new nonadentate lanthanide tag for the paramagnetic labelling of proteins. The tag can be easily synthesized and is stereochemically homogenous over a wide range of temperatures, yielding NMR spectra with a single set of peaks. Bound to ubiquitin, it induced large residual dipolar couplings and pseudocontact shifts that could be measured easily and agreed very well with the protein structure. We show that Cys-Ph-TAHA can be used to label large proteins that are biochemically challenging such as the Lac repressor in a 90 kDa ternary complex with DNA and inducer
A comparative study of palladium-gold and palladium-tin catalysts in the direct synthesis of H2O2
Herein we evaluate the promotive effect of Au and Sn incorporation into supported Pd nanoparticles for the direct synthesis of H2O2 from molecular H2 and O2. The introduction of both secondary metal modifiers was found to result in a significant enhancement in catalytic performance, although, in the case of the PdSn system, it was identified that relatively large quantities of the secondary metal were required to rival the activity observed over optimal Au-containing formulations, with the 0.25%Pd–2.25%Sn/TiO2 catalyst offering comparable H2O2 synthesis rates to the optimised 0.25%Pd–0.25%Au/TiO2 formulation. The introduction of Sn was found to considerably improve Pd dispersion, correlating with an improvement in selective H2 utilisation. Notably, the optimal PdSn catalyst identified in this work achieves superior H2O2 selectivities compared to the PdAu analogue and is able to rival the performance of state-of-the-art materials
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